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Practice Volumetric Chemical Analysis

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Republic of Iraq

Ministry 0f Higher Education and scientific Research

Al-Mustansiriya University

Collage of Science

Department of Chemistry

Practice Volumetric Chemical Analysis

First year / 2012

Edited by
Ruba Fahmi Abbas
Supervised by

Lecturer Dr. Lecturer Dr.

Mohammed Abdul-Hadi Khalil Alsouz Abbas Shebeeb Hasan Alkahdumi

1
2
Rules for the handing of reagents and solutions:-

1. Select the best available grade of chemical for analytical work.

2. Replace the top of every container immediately after the removal of reagent, do not
rely on someone else to do this.

3. Hold stoppers of reagent bottles between the fingers, stoppers should never be set on
the desk top.

4. Unless specifically directed to the country, never return any excess reagent or solution
to a bottle. The minor saving represented by the return of an excess is overshadowed by
the risk of contaminating the entire bottle.

5. Again, unless specifically directed otherwise, do not insert spoons, spatulas, or knives
into a bottle containing a solid chemical. Instead, shake the capped these are used
wherever possible in analytical work. Some suppliers label their products with the
maximum limits of impurity allowed by these specifications, other print the actual results
of analyses for the various impurities.

Quantitative Analysis:-

The quantitative chemical analysis is a scientific method to determine the absolute or

relative abundance of a chemical substance in a sample.

Volumetric Analysis (titrimetric analysis):-

Chemical procedure used for determining the concentration of a gas (evaluated or
consumed) in some reactions and solution by measured of it is volume A known volume
of a solution of unknown concentration is reacted with a known volume of a solution of
known concentration (standard solution). The standard solution is delivered not usually
from a burette so the volume added is known. This technique is known as titration. Often
an indicator is used to show when the correct proportions have reacted.

3
mmol standard solution = mmol unknown solution
M1 * V1 = M2 * V2

meq standard solution = meq unknown solution

N1 * V1 = N2 * V2

4
Primary standard solutions:-
Primary standard solutions are used in analytical chemistry. Including dissolving, a
primary standard is typically a reagent which can be weighed easily, and which is so
pure that its weight is truly representative of the number of moles of substance contained.
Features of a primary standard include:

1. High purity (more than 99.98%)

2. They have known formula and molecular weight
3. They are non-sensitive to atmospheric oxygen
4. High Stability (low reactivity for temperature, light, and dust)
5. High solubility (if used in titration)
6. High equivalent weight
7. Non-toxicity
8. Ready and cheap available
9. Should have high molecular weight for weighing errors are minimized
Secondary standard solutions:-
Secondary standard solutions are a solution that is not stable in its own form, and must
first be standardized before being used. A good example of this is NaOH, sodium
hydroxide is a secondary standard because it absorbs the moisture from the air than react
with CO2 in air to form Na2CO3 and its concentration wills changes. Features of
Secondary standards include: Influenced by atmosphere/environment
1. Concentration change over time
2. Usually powerful reactants
3. Usually cheap & easy to use
4.

1//Acid–base titration:-It is acid react with base to obtain salt and water:-

Acid + Base Salt + Water

An acid-base titration is the determination of the concentration of an acid or base by

exactly neutralizing the acid/base with an acid or base of known concentration. This
allows for quantitative analysis of the concentration of an unknown acid or base
solution. We must be chosen a suitable indicator , the equivalence point of the reaction,
the point at which equivalent amounts of the reactants have reacted. The point at which
the indicator changes color is called the end point.

5
 Indicator color

Indicator pH Acidity medium Basics medium

Methyl orange (M.O) 3.1 – 4.4 Red Yellow

Bromocresol Green 3.3 – 4.5 Yellow Blue

Methyl Red (M.R) 4.2 – 6.3 Red Yellow

Bromo Thymol Blue 6 – 7.6 Yellow Blue

Phenol Red (P.O) 6-8 Yellow Red

Cresol Indigo 7.4 - 9 Yellow purple

Phenol Phthalin (Ph. Ph) 8 – 9.8 Colorless Red

Thymol Blue 8 – 9.8 Yellow Blue

Experiment No.(1):- P reparation and standardization of 0.1 M(HCl)

hydrochloric acid solution
Theory:- Hydrochloric acid is produced in solutions up to 38% HCl (concentrated grade).
Higher concentrations up to just over 40% are chemically possible, but the evaporation
rate is then so high that storage and handling need extra precautions, such as pressure and
low temperature. Laboratory grade hydrochloric acid is not sufficiently pure to be used as
a primary standard, because it evaporates easily. In this experiment, a standard solution of
sodium carbonate is used to determine the exact concentration of a hydrochloric acid
solution. The neutralization reaction that occurs is as follows:
Na2CO3 + 2HCl  2NaCl + H2O + CO2
Methyl orange indicator solution is used. At the end-point – when neutralization just
occurs – the indicator changes color from yellow to peach-pink.

Procedure:-

1. Preparing (50 ml) 0.1 M HCl Solution:38 % HCL shows density 1.19 g/mL
and we can find M by next : -

sp.gr * % * 1000
M=
M.wt

Calculate the volume of HCl (conc.):- We must dilute it to preparing 0.1 M HCl in 50 ml
from next: (M* V) conc. = (M * V) dilute

M * V ml = 0.1 * 50 ml

6
Transfer V ml by cylinder to clean and dry beaker containing 30 ml D.W, transfer the
solution to volumetric flask capacity 50 ml, and complete the volume to the mark by D.W.

2. Preparing (50 ml) 0.1 M Na2CO3 Solution:-calculate amount from sodium carbonate
for prepare 0.1 M in 50 ml -

Wt.(gm)
M= * 1000
M.Wt. V(ml)

0.1 = Wt.(gm) * 1000

106 50

Wt. =0.53 gm

Weigh 0.53 gm. from Na2CO3 in clean and dry beaker and dilute in 30 ml D.W, transfer
solution to volumetric flask capacity 50 ml and complete the volume to the mark by D.W.

3. Transfer known volume of 5 ml the sodium

carbonate solution, with a pipette, to a conical
flask then add one or two drops of methyl
orange to this solution.

4. Add the acid unknown solution from the

burette gradually with continuous swirling of the
solution in the conical flask and near the end
point, the acid is added drop by drop. Continue
the addition of the acid until the color of the
solution passes from yellow to faint red.
5. Repeat the experiment three times and
tabulate your results then take the mean of the three readings.
Calculations: Calculate the molarity of HCl:-

m mol HCl = m mol Na2CO3

(M * V) HCl = (M * V) Na2CO3 * 1
2

( M * V burette) = ( 0.1 * 5) * 12

Discussion:-

1. What the difference between primary and secondary standard substances?

7
2. Calculate the volume of conc. HCl required for preparing 250 ml 0.1 M?
3. Calculate the weight of Na2CO3 required for preparing 100 ml 0.1 M?
4. Why is sodium carbonate primary solution?
5. Why standard solution should be colorless?
6. Why is HCl not primary solution?
7. What is the titration?
Experiment No.(2):- P reparation and standardization of 0.1 N sodium
hydroxide solution using Direct Titration
Theory:- Potassium hydrogen phthalate, often called simply KHP, is an acidic salt
Compound. It forms white powder, colorless crystals; it is solid and air-stable, making
it easy to weigh accurately. KHP is a useful standard for NaOH and Total Organic
Carbon (TOC) testing. Most TOC analyzers are based on the oxidation of organics to
carbon dioxide and water, with subsequent quantization of the carbon dioxide.
This experiment demonstrates the most common method for obtaining standard
solutions for titrimetric analysis. It involves preparation of a solution that has the
Approximate concentration desired determination of the concentration by direct
titration against a primary standard. We will standardize the 0.1 N NaOH solution
(the titrant) with potassium hydrogen phthalate (KHP, KC8H4O4H) using
phenolphthalein as the indicator. KHP is a weak acid and reacts with base in the
following way:-

C8H4O4H- + OH- C8H4O4-2 + H2O

Procedure:-

1.Preparation (50 ml)0.1N KHP:-

Wt.(gm) 1000
N= *
Eq.wt. V(ml)

Wt. = N* Eq.Wt * 0.05

= 0.1 * 204 * 0.05
= 1.02 gm

Weigh 1.02 gm from KHP and dilute in 30 ml D.W, transfer solution to volumetric flask
capacity 50 ml and complete the volume to the mark by D.W.

8
 2. Preparation (50 ml) 0.1 N NaOH :-

Wt.(gm) 1000
N= *
Eq.wt. V(ml)

Wt. = N* Eq.Wt * 0.05

= 0.1 * 40 * 0.05
= 0.2 gm

Weigh 0.2 gm from NaOH and dilute in 30 ml D.W, transfer solution to volumetric flask
capacity 50 ml and complete the volume to the mark by D.W.

3. Transfer 5 ml volume of the sodium hydroxide solution, with a pipette, to a conical

flask then adds one or two drops of phenolphthaline. The solution has the pink color
4. Add the (0.1 N KHP) from the burette gradually with continuous swirling of the
solution in the conical flask, and near the end point, the KHP is added drop by drop.
Continue the addition of the KHP until the color of the solution discharged.
5. Repeat the experiment three times and tabulate your results then take the mean of the
three readings.
Calculations:-Calculate the normality and % of NaOH:-

meq. NaOH = meq KHP

(N * V)NaOH = (N * V)KHP

Wt.
Eq.Wt * 1000 = ( N * V) KHP

Wt. V1 * V2 * V3
* 1000 = 0.1 *
40
3
Wt.
% NaOH = * 100
Wt. of sample

Discussion:-

1. Give 3 reasons why NaOH is not used as a primary standard?

2. Calculate ppm and ppt of KHP in this experiment?
3. Why is KHP used as a primary standard?
4. Why NaOH percentage less than 100%?
5. Why used ph.ph indicator?

9
 Experiment No (3):- Determination of Acetic Acid Content of Vinegar
Theory:- Determination of acetic acid concentration in commercially available white
vinegar is one of the simplest and easiest titrations. It is also possible to determine
concentration of acetic acid in other types of vinegar. The only problem is that the color
of the vinegar can make it difficult to spot the end point. However, in most cases even
vinegars made of red wine - after being diluted for titration - are pale enough so that the
phenolphthalein color at the end point can be easily spotted.
Vinegar can have different strengths. Most popular are concentrations between 4% and
15% In case of such concentrated solutions it may be impossible to simply take a single
sample for titration. We won't be able to measure such a volume of liquid with
reasonable accuracy, thus we are forced to dilute the original acid.

CH3COOH + NaOH → CH3COONa + H2O

Colorless Red

Acetic acid reacts with NaOH on the 1:1 basis

Procedure:-

1. Weigh accurately 5 ml volume of the Vinegar solution

2. Transfer to 300 ml conical flask and add 50 ml water free from CO2.
3. Add one or two drops of ph. ph. indicator to this solution.
4. Add 0.1 N NaOH from the burette gradually with continuous swirling of the solution
in the conical flask and near the end point, NaOH is added drop by drop. Continue the
addition of NaOH until the color of the solution passes from Colorless to faint red /pink.
5. Repeat the experiment three times and tabulate your results then take the mean of the
three readings
Calculations:- Calculate the rate of weighted percentages for Vinegar:-

0
 mole NaOH
m mol NaOH = m mol CH3COOH * mole CH COOH
3
Wt.
(M *Vburette ) NaOH = * 1000 * 1
M.Wt 1

(M * V) NaOH = 1000 * Wt. CH3COOH

60.05

Wt.% CH3COOH in vinegar = Wt. CH3COOH * 100

Wt. Wt. of vinegar

Wt. CH3COOH
Wt.% CH3COOH in vingar = *100
V V of sample (vingar)

Discussion:-

1. A word equation summarizing the souring of wine is:

Grain alcohol (C2H5OH) + oxygen → acetic acid + water.
Please convert this word equation to a balanced chemical equation.
2. Different vinegars may have different percentages of acetic acid. Is vinegar a mixture,
compound, or an element?
3. There are two kinds of vinegars, what the different between them?
Experiment No.(4):-Determination of acids in wines

Theory:-Acids are present in wine in many forms, but the largest percentage of acidity
comes from three primary types of acid: Tartaric acid, Malic acid, Citric acid. The chart
below provides guidelines for acidity based on the type of wine you are making.
Individual tastes vary, of course, so the information shown are recommendations only:-

Wine Style Recommended Acidity Range

Dry White Wine 0.65 % - 0.75 %
Sweet White Wine 0.70 % - 0.85 %
Dry Red Wine 0.60 % - 0.70 %
Sweet Red Wine 0.65 % - 0.80 %
Sherry Grape Wines 0.50 % - 0.60 %
Non-grape White Wines 0.55 % - 0.65 %
Non-grape Red Wines 0.50 % - 0.60 %
Procedure:-

1. Pipette 50 ml from wines into 250 ml conical flask

2. Add 50 ml of D.W
3. Add 2 drops of Ph.Ph. indicator.
4. Titrate with standard 0.1 N NaOH till the color change to pink
Calculation: Express the acidity of the wines as percent (w/v) tartaric acid C2H4O2
(COOH)2 (fw=150.09):-

m eq NaOH = m eq tartaric acid

Wt.
(N * Vburette) NaOH =
Eq. Wt. *1000

Wt.
0.1 * V = *1000
Eq. Wt.

Wt. % Wt. tartaric acid

= V of wines * 100
V

Discussion:-

1. What is the formula of tartaric acid, malic acid and citric acid?
2. What are the primary types of acid in wines?
3. Why choice the ph.ph indicator?
Experiment No.(5):- Determination of Malic acid in Tomatoes

Theory:- The type of acid is found in tomato sauce is mostly Citric acid
and Malic acid at a 1 to 0.6 ratio respectively in the ripe red fruit. In the
green fruit the ratio is 1 to 1.3 Malic acid is an organic compound with
the formula HO2CCH2CHOHCO2H. It is a dicarboxylic acid which is
made by all living organisms, contributes to the pleasantly sour taste of
fruits, and is used as a food additive.

Procedure :-

1. Use a clean and dry safety pipette. Draw up 10 ml of tomato sauce and discharge it
into a 50 ml volumetric flask, and complete the volume to the mark with D.W.
2. Transfer the solution to the conical flask, Add 3 drops of phenolphthalein indicator.
3. Titrate with standard 0.1 N NaOH until the color changes from colorless to pink
Calculation: Express the acidity of the tomatoes sauce as percent (w/v) Malic acid
C4H6O5 (fw= 134.09):-

m eq NaOH = m eq malic acid

Wt.
(N * Vburette) NaOH =
Eq. Wt. *1000

Wt.
0.1 * V = *1000
Eq.Wt.

Wt. % = Wt. malic acid * 100 = Wt. *100

V V of tomato sause 10

Discussion:-

1. What type of acid is found in tomato sauce?

2. What is the formula of Malic acid?
3. What is the deference between malic acid and acetic, sulfuric acid?
Experiment No.(6):- Determination of Ammonia in Ammonium salt
Theory:- Ammonia is a very toxic gas, what you buy in the store as "ammonia" is a very
dilute solution of ammonia in water. When dissolved in water, it forms a very alkaline
solution (it is actually ammonium hydroxide, NH4OH) that is an excellent solvent for
non-polar molecules like oils.
Two methods: 1. the direct method, a solution of the ammonium salt is treated with a
solution of a strong base (NaOH) and the mixture distilled. Ammonia is quantitativty
expelled, and is absorbed in an excess of standard acid (HCl).

NH4+ + NaOH NH4OH + Na+

NH4OH + HCl NH4Cl + H2O

2. Indirect method, a solution of the ammonium salt is treated with formaldehyde to

prepare hexa amine compound

NH4Cl + 6HCHO (CH2)6N4 +HCl

hexa amine compound is weak base titrate with standard solution is NaOH.
Procedure:-
1. Weigh accurately 1 gm from ammonium chloride.
2. Dissolve salt in 100 ml D.W and transfer to conical flask capacity 200 ml, and
complete the volume to the mark.
3. Transfer 5 ml from solution, with a pipette, to a conical flask. Capacity 300 ml.
4. Add 25 ml from D.W with a pipette.
5. Add 3 -4 drops from ph.ph indicator, and titrate the solution against (0.1 N NaOH), till
the color change to pink.
6. Repeat the experiment three times and tabulate your results then take the mean of the
three readings.
Calculations:-Calculate the normality and % of ammonium chloride:-

(N * V)NaOH = (N * V) NH4Cl

(N * V) NaOH = Wt. * 1000

Eq.wt

(0.1 *V ) = Wt. * 1000

34

Wt.
Wt. % NH3 = *100
Wt. Wt. of sample

Discussion:-

1. What is Ammonia?
2. What is hexa amine compound?
3. What is the different between ammonia and ammonium hydroxide?
Experiment No.(7):- Determination of the relative molecular mass of an
organic acid
Theory:- Many of the common carboxylic acids are readily soluble in water and can be
titrated with sodium hydroxide or potassium hydroxide solutions. For sparingly soluble
organic acids the necessary solution can be achieved by using a mixture of ethanol and
water as solvent. But for determinations carried out in aqueous solutions it is not
normally possible to differentiate easily between the end points for the individual
carboxylic acid groups in diprotic acids, such as succinic acid, as the dissociation
constants are too close together. In these cases the end points for titrations with sodium

4
hydroxide correspond to neutralization of all the acidic groups. As some organic acids
can be obtained in very high states of purity, sufficiently sharp end points can be
obtained to justify their use as standards,e.g. benzoic acid and succinic acid.
The titration procedure described in this section can be used to determine the relative
molecular mass (R.M.M.) of a pure carboxylic acid (if the number of acidic groups is
known) or the purity of an acid of known R.M.M.

Procedure:-

1. Weigh out accurately about 4 g of the pure organic acid, dissolve it in the minimum
volume of water (Note 1), or 1:1 (v/v) ethanol/water mixture, and transfer the solution to
a 250 mL graduated flask.

2. Ensure the solution is homogeneous and make up to the required volume. Use a
pipette to measure out accurately a 25 mL aliquot and transfer to a 250 mL conical flask.

3. Using two drops of phenolphthalein solution as indicator titrate with standard 0.2M
(approx.) sodium hydroxide solution (Note 2) until the colorless solution becomes faintly
pink.

4. Repeat with further 25 mL volumes of the acid solution until two results in agreement
are obtained.

Calculation:- The relative molecular mass is given by:

1000 W * P
R.M.M =
10 V * M

Where:-
W= is the weight of the acid taken,
P= is the number of carboxylic acid groups,
M= is the molarity of the sodium hydroxide.
V= is the volume of sodium hydroxide used, and
**Notes. (1) In order to obtain sharp end points all de-ionized water used should be
carbon-dioxide-free, as far as is possible.
(2) Volumes of 0.2M sodium hydroxide required will normally be in the range from
about 15 mL to 30 mL depending upon the nature of the organic acid being
determined.
Discussion:-
1. What is the difference between R.M.M and molecular weight?
2. Why does the titration taken in (1:1) ethanol: water medium?
3. Write equation to express this titration?
Experiment No.(8):- Determination of the equivalent weight of a weak
acid
Theory:- The equivalent weight of an acid, which is an aid in establishing it is identity,
is readily determined by titrating a weighed quantity of the purified acid with standard
sodium hydroxide.

Procedure:-

1. Weigh 0.1 mg individual samples into 250 ml conical flask.

2. Dissolve in 50-75 ml D.W (see note).
3. Add 2 drops of ph.ph indicator.
4. Titrate with standard base to the first persistent (30 sec.) color of the indicator.
Calculation:-Calculate the equivalent weight of the acid:-

M.Wt of acid
Eq. Wt. of acid =
no. of proton (H+)

**note: acids with limited solubility in water may dissolve more readily in ethanol
or an ethanol-water mixture. The alcohol may be measurably acidic and should be
rendered faintly alkaline to ph.ph before it is used as a solvent. As excess of
standard base, the excess being determined by back-titration with standard acid.

Discussion:-

1. The weight of H2C2O4 is 0.5 gm dissolved in 100 ml D.W, what the normality of
H2C2O4?
2. What are the Eq. Wt of acetic acid, H2SO4, oxalic acid and H3PO4?
3. What are the Eq. Wt. of malic acid, tartaric acid and arsenic acid?

6
 Experiment No.(9):- Back titration
Theory:- Direct titration involves the direct and stepwise addition of a standard titrant to
the analyte whilst the back titration involves reacting a standard excess titrant with an
analyte solution of an unknown concentration, then reacting the excess (left over) titrant
with an analyte of known concentration to determine the concentration of excess titrant.
While In back titration we use two reagents (standard solution) - one, that reacts with
the original sample (let's call it A, first standard solution ), and second (lets call it B ,
second standard solution), that reacts with the first reagent, We add precisely measured
amount of reagent A to sample and once the reaction ends we titrate excess reagent A left
with reagent B. Knowing initial amount of reagent A and amount that was left after the
reaction (from titration) we can easily calculate how much reagent A was used for the
first reaction. In this test, we want to find normality for nitric acid, so we added excess
amount from NaOH , and the excess amount from NaOH back titration with standard
solution like HCl.

HNO3 + NaOH NaNO3 + H2O + NaOH excess

NaOH + HCl ph.ph

excess NaCl + H2O
pink colorless

Procedure:-
1. Transfer 5 ml volume of the nitric acid solution to a conical flask.
2. Transfer 7 ml volume of the 0.1 N NaOH solutions to the same conical flask.
3. Add one or two drops of ph.ph to this solution and complete the titration with (0.1 N
HCl) comes from the burette until the color change from pink to colorless.
4. Repeat the experiment three times and tabulate your results then take the mean of the
three readings.

Calculations :-Calculate the normality of nitric acid:-

(N *V)HNO3 = (N *V)NaOH - (N *V) HCl

(V1 *V2 *V3)

(N *5) = (0.1 * 7) - [ (0.1 * ]
3

Discussion:-1. What difference between HCl and HNO3?

1. How does back titration differ from a direct titration?
2. Why is a back titration sometimes used for an analysis rather than a direct titration?
 Experiment No.(10):- Determination of Na2CO3 content of washing soda
Theory:-Chemically, washing soda is known as sodium carbonate. It is also often
referred to as soda ash or soda crystals. Washing soda is a sodium salt and is obtained
from carbonic acid. It is widely available in the form of a white powder. It is mostly
found in a crystalline form as a heptahydrate (where each sodium carbonate molecule
is bonded with seven molecules of water). On exposure to air, it loses the water
molecules to form a monohydrate. When it dissolves in water, its molecules break
down and ions of sodium and carbonate are released. Washing soda is a key
component of laundry soaps and other household cleaning products as it can easily
remove dirt and tough greasy stains from clothes, utensils, floors, and various other
surfaces. It is also used as a cleansing agent for removing dirt stuck on silver and glass
items. When it is dissolved in water, the solution acts as a fungicide that can kill mold
and mildew in the damp areas of the house. Water in the swimming pools turns acidic
due to repeated addition of chlorine as a disinfectant. Washing soda is added to this
water to make it chemically neutral.
Procedure:-

1. Weigh out accurately about 3.6 g of the washing-soda crystals, dissolve in water, and
make up to 250 mL in a graduated flask. Mix thoroughly.

2. Titrate 25 mL of the solution with standard hydrochloric acid of approximately 0.1 M

concentration using methyl orange, or, better, methyl orange-indigo carmine or
bromocresol green as indicator. Two consecutive titrations should agree within 0.05 mL.
Calculation:-The weight of anhydrous sodium carbonate, Na2CO3, which has reacted
with the standard hydrochloric acid, can be readily calculated from the equation:

Na2CO3 + 2HC1 = 2NaC1 + H2O + CO2

106.01 2 x 36.46
The percentage of Na2CO3 can then be calculated from the known weight of washing
soda employed. A simpler and more general procedure is illustrated by the following
example.

Weight of weighing bottle + substance = 16.79 10 g

Weight of weighing bottle + residual substance = 13.0110 g Weight of sample used =
3.7800 g, this was dissolved in water and made up to 250mL.
Titration of 25.00 mL of the carbonate solution with 0.1060M HC1, using methyl
orange—indigo carmine as indicator.

l mL 1M HC1 = 0.05300g Na2CO3

 25.93 x 0.1060 = 2.749 mL 1M HC1

2.749 x 0.05300 = 0.1457 g Na2CO3 in portion titrated.

Weight of washing soda in portion titrated = 3.7800 x 25.0/250 = 0.3780 g

Percentage of Na2CO3 = 0.1457 x 100/0.3780 = 38.54 per cent

Discussion:-

1. What is the washing soda?

2. Why the washing soda contains Na2CO3?
3. Which the must indicator used in this experiment?
Experiment No.(11):- Determination of two acids in Soda By Titration
Theory:- In this experiment, we will determine the concentration of carbonate and
bicarbonate species in sodas using the technique of titration. A primary standard used
in this experiment is NaOH for the direct titration of the diprotic acid. A diprotic acid is
an acid that yields two H+ ions per acid molecule. Examples of diprotic acids are
sulfuric acid, H2SO4, and carbonic acid, H2CO3, Color indicators which utilize changes
in pH will be used to determine the presence of the different species of the acid.
Procedure:-

1. 0.2 g of NaOH pellets were placed in a 50mL volumetric flask and diluted to
the mark with distilled water to make an approximate 0.1M solution.
2. 25 mL of each cold, fresh soda was measured in a graduated cylinder.
3. The sample was then placed in a beaker
4. 5 drops of Methyl orange indicator was added to the solution
5. The solution was titrated with NaOH until Color of this indicator changes from
yellow to orange to red at pH between 3.1 and 4.4.
Calculations:-Calculate the normality of diprotic acid in soda:-

(N * V) diportic acid = (N * V) NaOH

N * 25 = 0.1 * V burette

Calculate ppm for Na2CO3 and NaHCO3

ppm Na2CO3 = N * Eq.WT. *1000

 ppm NaHCO3 = N * Eq.WT. *1000

Discussion:-

1. What is diprotic acid?

2. Calculate molarity of diprotic acid?
3. What is primary standard used in this experiment?
4. Which organic acids or mineral acids are stronger, why?
Experiment No.(12):- Double titration
Theory:-Double titration is a process was the first titration is used to standardize a
titrant and the second titration is used to find the molarity of the unknown solution.
A:-Analysis of commercial caustic soda:-
Consider a mixture of NaOH(aq) and Na2CO3(aq). Reaction between HCl(aq) and
Na2CO3(aq) takes place in two stages:-
HCl(aq) + Na2CO3(aq) ⎯→ NaHCO3(aq) + H2O(l) ………………. (1)

Cl-(aq) + NaHCO3(aq) ⎯→ NaCl(aq) + CO2(g) + H2O(l) ………….. (2)

While that between HCl(aq) and NaOH(aq) completes in only one step:-

HCl(aq) + NaOH(aq) ⎯→ NaCl(aq) + H2O(l) …………….……….. (3)

Reactions (1) and (3) can be indicated by phenolphthalein and that of reaction (2) can
be indicated by methyl orange.
Reaction 1 and 3 Evidenced by the first equivalence point between standard solution
and both of OH- and half CO3-2 by using Ph.Ph. indicator, Directory where the color
changes from red to colorless. For The remaining half from CO3-2 , added to solution
M.O indicator and complete titration with HCl , the color change from yellow to pink
and we can see that in reaction (2).
In another method the total alkali (carbonate + hydroxide) is determined by titration with
standard acid, using methyl orange as indicator. In a second portion of solution the
carbonate is precipitated with a slight excess of barium chloride solution, and, without
filtering, the solution is titrated with standard acid using Ph.Ph as indicator. The latter
titration gives the hydroxide content, and by subtracting this from the first titration, the
Volume of acid required for the carbonate is obtained:-

Na2CO3 + BaCl2 BaCl2 + 2NaCl

0
Procedure:-

1. Transfer 5 ml volume of the mixture solution, with a pipette, to a conical flask then
add one or two drops of Ph.PH to this solution and titrate with ( 0.1N HCl) come from
the burette gradually with continuous swirling of the solution in the conical flask and
near the end point, the acid is added drop by drop. Continue the addition of the acid until
the color of the solution passes from red to colorless, record the volume for acid as V1.
2. add one or two drops of methyl orange to this solution and complete the titration
with ( 0.1 N HCl) come from the burette until the color change from yellow to pink ,
record the volume for acid as V2.
3. Repeat the experiment three times and tabulate your results then take the mean of the
three readings.
Calculations:-A-Calculate the normality and percentages of OH- in mixture:-

(N * V) HCl = (N * V) NaOH

0.1 * (V1 - V2)burette = N * 1000

N *Eq.Wt
% NaOH = * 100
Wt. of Sample

B-Calculate the normality and percentages of CO3-2 in mixture:-

(N * V) HCl = (N * V) Na2 CO3

(0.1 * 2 V2) burette = N * 1000

N *Eq.Wt
% Na2CO3 = * 100
Wt. of Sample

Discussion:-
1.What is the caustic soda?
2.What is double titration?
3.Why ph.ph indicator used first?
4. Why After addition barium chloride we just use ph.ph indicator ?
 B:-Determination carbonate and bicarbonate in mixture:-
Sodium bicarbonate or sodium hydrogen carbonate is the chemical compound with the
formula Na HCO3. Sodium bicarbonate is a white solid that is crystalline but often
appears as a fine powder, the salt has many related names such as baking soda, bread
soda, cooking soda, and bicarbonate of soda.
This experiment Consider a mixture of carbonate and bicarbonate are titrating with
standard solution (0.1 N HCl) by using ph.ph and methyl orange as indicator , after
adding ph.ph indicator half of carbonate converted to bicarbonate, but after adding
M.O indicator the bicarbonate and half of carbonate converted to H2CO3 . The H2CO3
Disintegrate to CO2 and H2O.

Na2CO3 ph.ph NaHCO3

+ HCl + NaCl
NaHCO3 NaHCO3
pH=9.5 pink pH=8.4 colorless

NaHCO3 H2CO3
+ 2HCl + 2NaCl
NaHCO3 H2CO3
pH=8.4 yellow
pH=4.4 pink

H2CO3 CO2 +H2O

Procedure:-

1. Transfer 5 ml volume of the mixture solution, with a pipette, to a conical flask then
add one or two drops of Ph. Ph to this solution and titrate with ( 0.1 N HCl) come from
the burette gradually with continuous swirling of the solution in the conical flask and
near the end point, the acid is added drop by drop. Continue the addition of the acid until
the color of the solution passes from red to colorless, record the volume for acid as V1.
2. add one or two drops of methyl orange to this solution and complete the titration
with ( 0.1 N HCl) come from the burette until the color change from yellow to pink ,
record the volume for acid as V2.

3. Repeat the experiment three times and tabulate your results then take the mean of the
three readings

Calculations:-

A- Calculate the normality and rate percentages of bicarbonate in mixture:-

 (N * V) HCl = (N * V)NaHCO3

0.1 * (V2 - 2V1)burette = N * 1000

N *Eq.Wt
% NaHCO3 = * 100
Wt. of Sample

B- Calculate the normality and rate percentages of CO3-2 in mixture:-

(N * V) HCl = (N * V) Na2 CO3

(0.1 * 2 V1)burette = N * 1000

N *Eq.Wt
% Na2CO3 = * 100
Wt. of Sample

Discussion:-

1. What is Sodium bicarbonate? What is the basicity difference between NaHCO3 and
NaOH?
2. What is the difference between V1 and V2 in experiment A and experiment B?
3. Calculate the conc. Of Na2CO3 and NaHCO3 by ppm?
Experiment No.(13):-Determination of bicarbonate in blood by back
titration
Theory:- About 95% of the total carbon dioxide in human blood exists as HCO3-, the
remainder existing as dissolved CO2. The HCO3- concentration, for most clinical work,
can be used as a diagnostic aid. It is determined by adding an excess of 0.01 M HC1, to
volatilize the HCO3- as CO2, swirling to allow the CO2 to escape, and then back-titrating
the excess HC1 with 0.01 M NaOH. The 0.01 M HCI and, NaOH solutions are prepared
by diluting standardized 0.1 M solutions.

HCO3- + H+ H2O +CO2

excess H+ +OH- H2O

 Note: The sodium hydroxide solution is a secondary standard, and any errors in standardizing
will be represented in the standardizing of the hydrochloric acid, the sodium hydroxide should be
used within one week of standardization. If this experiment is done before Experime nt 6, this
procedure can be used to standardize the sodium hydroxide solu6on for that experiment.

Procedure:-Solutions and Chemical's Required:-

1. Provided. 0.1% Phenol red (phenolsulfonaphthalein) solution in 0.003 M NaOH, 1%
saline (NaC1) solution in CO2-free water, Anti- foam A (Dow Corning Corp.)
2. To prepare. Standard 0.1 M and 0.01 M HC1 and 0.1 M and 0.01 M NaOH solutions.
The molarity of the standard HC1 and standard NaOH needs to be known only to three
significant figures. Prepare 250 mL standard 0.1M NaOH. Since only three significant
figures are required, you may use one-tenth the amount of KHP for titration, in which
case the end point will occur at about 4.0 to 4.5 mL. A 10-mL burette should be used in
these titrations. Standardize a 0.1 M HC1 solution by titrating 5.00 mL of it with the
standard 0.1M NaOH. The phenol red indicator may be used. If you have only a standard
01 M HC1 solution, use this to standardize 0.1 M NaOH solution.
Prepare 500 mL of 0.01 M HC1 and 0.01 M NaOH solutions by diluting 50 mL of the
0.1 M solutions to 500 mL with the saline solution. These should be prepared fresh on
the day of use. The saline aids in the volatilization of the CO2 from the acidified solution
by decreasing its solubility.
Things to do before the Experiment:-Prepare and standardize the 0.1 M HC1 and 0.1 M NaOH.
This will require drying primary standard KHP ahead of time if either standard HCI or NaOH is
not available.

 The work:-

1. Preparation of the sample. Either serum or plasma (oxalated or heparinized) may be

used for the determination. This may be freshly drawn blood from an animal. (Do not do
this yourself; your instructor will supply the sample.) See Chapter 1 for a discussion of
the differences between serum, plasma, and whole blood. A 10- to 15-mL sample (20 to
30 mL whole blood) should be adequate for triplicate determinations by a class of 30
students. Fluoride should be added to prevent glycolysis, or breakdown of glucose,
which can change the pH. The fluoride inhibits the enzyme catalysis causing glycolysis
and stabilizes the pH for about 2 h. The tube used for collecting the sample can be rinsed
with a solution of 100 mg sodium heparin plus 4 g sodium fluoride per 100 mL. The
sample should be kept anaerobically, that is, stoppered to keep out atmospheric CO.
Since the analysis should be done on the day the blood is drawn, the solutions should be
prepared ahead of time.

4
2. Preparation of comparison solution. Prepare a standard for color comparison at the end
point as follows. Place 6 mL of 1% saline solution in a 25-ml conical flask and add 0.10
mL serum or plasma. Add two drops phenol red indicator, insert a stopper, and rotate
gently to mix the contents. The transition range of this indicator is pH 8.4 to 6.7 (yellow
to red). Because of the buffering capacity of the blood, the end point occurs in this range.

3. Titration of the sample. The pooled serum or plasma sample will have been prepared
by touching the end of a stirring rod and rotating it in the pooled sample. This will
prevent excess foaming when the sample is swirled. Place 0.100 mL of serum or plasma
a in a 25-mL Erlenmeyer.
Note: This determination may be performe d on a macro scale using 5.00 mL acid and 1.00 mL
sample, or using2.00 mL acid and 0.500 mL sample. In the former case, the back-titration will
require about 2.4 mL of 0.01M NaOH, and in the latter case, about 0.7 mL. Flask and add 1.00
mL of 0.01 M HC1 and 4 mL of 1% saline. Swirl the flask vigorously for at least 1 mm to allow
the CO2 to escape. Add two drops of indicator and then titrate with 0.01 M NaOH drop wise, but
rapidly, until a pink color matching the standard persists for at least 15 S. The NaOH may be
added carefully with a graduated 1-mL measuring pipet and read to the nearest 0.01 mL.

The normal value of blood bicarbonate is about 26 meq/L (25 to 32 meqlL), or 0.026 me q/mL.
Meq HCO3 = mmol HCO3 . Since 0.1 mL blood was taken for analysis, it should consume about
0.0026 mmol HC1, or 0.26 mL of 0.01 M HCI. Hence, since 1 mL of 0.01 M HC1 was taken, about
0.74 mL should re main unreacted, and the back-titration should take about 0.7 mL of 0.01 M
NaOH.

Discussion:-

1. What is the blood and what does contains?

2. What is the blood pH, why it must be constant?
3. What is the saline solution, why it gives to patent?
4. What is the type of indicator used in this work, why?
2// Precipitation titration:-
Volumetric methods based upon the formation of sparingly soluble precipitate are called
precipitation titration; different titrimetric procedures that take place in solution were
discussed. A special type of titrimetric procedures involves the formation of precipitates
during the course of a titration. The titrant reacts with the analyte forming an insoluble
material and the titration continues till the very last amount of analyte is consumed. The
first drop of titrant in excess will react with an indicator resulting in a color change and
announcing the termination of the titration. Precipitation titration is a very important;
because it is a perfect method for determine halogens and some metal ions. There are
three kinds (types) of indicators used in precipitation titration, the first used K2CrO4
(mohr, formation color precipitation method), the second used fluorescein indicator
(fajan method), and the third used Fe+3 ion as indicator (volhard method back- titration
formation color complex method).

Experiment No.(14):- Preparation and standardization of 0.1 N AgNO3

solution with sodium chloride (Mohr Method)
Theory:-The Mohr method uses chromate ion as an indicator in the titration of chloride
ion with silver nitrate. The first excess of titrant results in the formation of a red silver
chromate precipitate, which signals the end point.

Ag+ +X- AgX+ NaNO3

AgNO3 +NaCl AgCl + NaNO3

2AgNO3 +K2CrO4 AgCrO4 + 2KNO3

yellow
red ppt.

Procedure:-
1-Standardization of silver nitrate solution:-Sodium chloride has a relative molecular
mass of 58.44. A 0.05 M solution is prepared by weighing out 0.29 g of the pure dry salt
and dissolving it in 50 mL of water in a volumetric flask.

2. Preparation approximately 0.1 N AgNO3: calculate the Wt. in 50 ml of AgNO3 from:-

Wt. 1000
N= *
Eq.Wt. V (ml)

Wt. * 1000
0.05 =
169 50

Weigh X g of AgNO3 in dry and clean beaker then transfer to 50 ml volumetric flask
and complete the volume to the mark with D.W.
3. Transfer 5 ml volume of the(0.02 N NaCl) solution, with a pipette, to a conical flask.
Capacity 300 ml.
4. Add 4-5 drops of potassium chromate indicator K2CrO4 to this solution.
5. Add (0.05 N AgNO3) from the burette gradually with continuous swirling of the
solution in the conical flask and near the end point, AgNO3 is added drop by drop.
Continue the addition of AgNO3 until appears red Precipitate.

6
6. Repeat step 2 three time to take the average of volume (V).
7. Find the error of titration process by Transfer 5 ml volume of the D.W, with a pipette,
to a conical flask. capacity 300 ml, add 4-5 drops of potassium chromate indicator
K2CrO4 to this solution, Add (0.05 N AgNO3) from the burette gradually with
continuous swirling of the solution in the conical flask and near the end point, AgNO3
is added drop by drop. Continue the addition of AgNO3 until upper red Precipitate
appears, Recorded the volume (V1).
Calculations :-Calculate the normality of Cl-:-

(N * V)NaCl = (N * V) AgNO3
(N * 5) = (0.05 *V -V1)
conc.(gm/L)Cl- = N * Eq.Wt

Discussion:-

1. What is the red precipitate?

2. What is the name of indicator?
3. What is the error of titration process?
4. What the second name of this method?
5. Why AgCl Precipitate first than Ag2CrO4?
6. Why AgNO3 solution must be standardized first?
Experiment No.(15):- Determination of Chloride by Volhard's Method
(back titration)
Theory:- This method uses a back titration with potassium thiocyanate to determine the
concentration of chloride ions in a solution. Before the titration an excess volume of a
silver nitrate solution is added to the solution containing chloride ions, forming a
precipitate of silver chloride. The term ‘excess‘ is used as the moles of silver nitrate
added are known to exceed the moles of sodium chloride present in the sample so that all
the chloride ions present will react.

Ag+(aq) + Cl-(aq) AgCl(s) + Ag+ excess

The indicator Fe3+ (ferric ion) are then added and the solution is titrated with the
potassium thiocyanate solution. The titrate remains pale yellow as the excess (unreacted)
silver ions react with the thiocyanate ions to form a silver thiocyanate precipitate.

Ag+(aq) excess + SCN -(aq) AgSCN(s)

Once all the silver ions have reacted, the slightest excess of thiocyanate reacts with Fe3+ to
form a dark red complex.
 Fe3+(aq) + SCN -(aq) [FeSCN]2+(aq)

Procedure:-
1. Weigh 0.2 mg NaCl or KCl, Transfer to a conical flask capacity 250 ml and Dissolve
in 50 ml D.W.
2. Added 5-6 drops (6N HNO3).
3. Added 2 ml nitrobenzene.
4. Add excess (V1 ml) 0.05 N AgNO3 by pipette.
5. Add to the conical flask 2 ml from (mohrs salt) Ferric ammonium sulfate solution
NH4Fe (SO4)2.12H2O, and titrate with 0.05 N potassium thiocyanate KSCN until upper
red/ bloody color appears, Record the volume (V2).

Calculations :-Calculate the volume of excess AgNO3:-

mEq Cl- = m Eq AgNO3 - mEq SCN-

Wt.
*1000 = (N * V) - (N * V)
Eq.Wt

Wt.
*1000 = (0.05 * V1 pipette)
- (0.05 * V2 burette)
35.40

Wt. Cl-
%Cl - = * 100
Wt. sample

Wt.
= *100
0.2 g

When 0.03546 = eq.wt. for chloride ion.

Discussion:-
1. What is back titration?
2. Why nitro benzene is added?
3. What is indicator in this test?
4. Why the nitric acids are added?
5. What is the other name of this method?
 Experiment No.(16):- Determination of Chloride by Fajan’s method
(Adsorption indictors)
Theory:-In Fajan method, the end point is detected with a dye that imparts a distinctive
color to the silver chloride precipitate. Dichlorofluorescein or Fluorescein (HIn) is
commonly used as indicator. As the surface equivalence point is approached and passed,
silver ion will become the primary adsorbed the surface of precipitate. The negatively
charged dichlorofluorescein or Fluorescein anion (In-) will then on displaces the nitrate
ion to become the countering. On being adsorbed, its electronic changes so that it
reflects reddish /pink light rather than yellow-green, this signals the end point.

AgCl: Ag+/NO3-(s) + HIn (yellow) → AgCl:Ag+/In- (pink) + H+ + NO3-

Procedure:-

1. Transfer 25 ml volume of the NaCl or KCl solution, with a pipette, to a conical flask.
2. Add 5-10 drops Dichlorofluorescein or Fluorescein and 0.1 gm dextrin solution. The
color of solution becomes yellow-green.
3. Add 0.0.5 M AgNO3 from the burette gradually with continuous swirling of the
solution in the conical flask and near the end point, AgNO3 is added drop by drop.
Continue the addition of AgNO3 until appears reddish Precipitate
Calculations:-Calculate the molarity of chloride:-

(M * V)Cl- = (M * V) AgNO3
Calculate PCl:- PCl = - Log [Cl-]
-

Discussion:-

1. What is the HIn?

2. Define adsorbed process?
3. What is the adsorbed indicator?
4. Why dextrin solution is added?
5. What is the name of precipitation involved Ag?
6. Why the used indicator is called Fluorescein indicator?
 Experiment No.(19):- Determination of potassium
Theory:-Potassium may be precipitated with excess of sodium tetraphenylborate
solution as potassium tetraphenylborate. The excess of reagent is determined by titration
with mercury (II) nitrate solution. The indicator consists of a mixture of iron (III) nitrate
and dilute sodium thiocyanate solution. The end-point is revealed by the decolorisation
of the iron (III)-thiocyanate complex due to the formation of the colorless mercury (II)
thiocyanate. The reaction between mercury(II) nitrate and sodium tetraphenylborate
under the experimental conditions used is not quite stoichiometric; hence it is necessary
to determine the volume in mL of Hg(NO3)2 solution equivalent to 1 mL of a
NaB(C6H5 )4 solution. Halides must be absent.

Procedure:-

1. Prepare the sodium tetraphenylborate solution by dissolving 6.0 g of the solid in

about 200 mL of distilled water in a glass-stoppered bottle.

2. Add about 1 g of moist aluminum hydroxide gel, and shake well at five-minute
intervals for about 20 minutes. Filter through a Whatman No. 40 filter paper, pouring
the first running's back through the filter if necessary, to ensure a clear filtrate.

3. Add 15 mL of 0.1 M sodium hydroxide to the solution to give a pH of about 9,

then make up to 1 L and store the solution in a polyethelene bottle.

4. Prepare a mercury(II) nitrate solution (0.03M) by dissolving 10.3 g

recrystallized mercury(II) nitrate, Hg(N03)2,H20, in 800 mL distilled water containing
20 mL 2M nitric acid. Dilute to 1 L in a graduated flask and then standardize by
titrating with a standard thiocyanate solution using iron (III) indicator solution.

5. Prepare the indicator solutions for the main titration by dissolving separately 5
g hydrated iron (III) nitrate in 100 mL of distilled water and filtering, and 0.08 g
sodium thiocyanate in 100 mL of distilled water.

6. Standardization. Pipette 10.0 mL of the sodium tetraphenylborate solution into

a 250 mL beaker and add 90 mL water, 2.5 mL 0.1 M nitric acid, 1.0 mL iron (III)
nitrate solution, and 10.0 mL sodium thiocyanate solution. Without delay stir the
solution mechanically, and then slowly add from a burette 10 drops of mercury (II)
nitrate solution. Continue the titration by adding the mercury (II) nitrate solution at a
rate of 1—2 drops per second until the color of the indicator is temporarily discharged.
Continue the titration more slowly, but maintain the rapid state of stirring. The end
point is arbitrarily defined as the point when the indicator color is discharged and fails
to reappear for 1 minute. Perform at least three titrations, and calculate the mean

0
 volume of mercury (II) nitrate solution equivalent to 10.0 mL of the sodium
tetraphenylborate solution.

7. Pipette 25.0 mL of the potassium ion solution (about 10mg K+) into a 50 mL
graduated flask; add 0.5 mL 1 M nitric acid and mix. Introduce 20.0 mL of the sodium
tetraphenylborate solution, dilute to the mark, mix, and then pour the mixture into a
150 mL flask provided with a ground stopper. Shake the stoppered flask for 5 minutes
on a mechanical shaker to coagulate the precipitate, and then filter most of the solution
through a dry Whatman No. 40 filter paper into a dry beaker. Transfer 25.0 mL of the
filtrate into a 250 mL conical flask and add 75 mL of water, l.0mL of iron (III) nitrate
solution, and 1.0mL of sodium thiocyanate solution. Titrate with the mercury(II)
nitrate solution as described above.
**Note. This determination is only suitable for students with analytical experience and should
not be attempted by beginners.

Calculation:-

mmol K+ = mmol NaB(C6H5)4 - mmol Hg(NO3)2

(M *V) = (M * V) - ( M * V)

ppm K+ = M * A.Wt. *1000

Discussion:-

1. Why add NaSCN and HNO3 are added?

2. Write the chemical equation for the titration?
3. What is the chemical formula of tetraphenylborate ?
4. Why NaOH is added and store in a polyethelene bottle?
5. Why aluminum hydroxide gel is added? What it is chemical formula?
Experiment No.(18):-Determination of silver in silver alloy
Theory:- A commercial silver alloy in the form of wire or foil is suitable for this
determination.
Procedure:-

1. Clean the alloy with emery cloth and weigh it accurately.

2. Place it in a 250 mL conical flask, add 5 mL water and 10 mL concentrated
nitric acid; place a funnel in the mouth of the flask to avoid mechanical loss.
3. Warm the flask gently until the alloy has dissolved. Add a little water and boil
for 5 minutes in order to expel oxides of nitrogen.
4. Transfer the cold solution quantitatively to a 100 mL graduated flask and make
up to the mark with distilled water.
5. Titrate 25 mL portions of the solution with standard 0.1 M thiocyanate.
Calculation:-

mmol Ag+ = mmol KSCN

Wt.
* 1000 = M *V
A. Wt.

Wt.
* 1000 = 0.1 *V burette
A. Wt.

Wt. Ag
% Ag in Alloy = *1000
Wt. of sample

Discussion:-

1. Why HNO3 acid is added?

2. Write the chemical equation express the titration reaction?

3. Ag common with two metal in uses, what the other two metals?

3//Reduction - Oxidation titration (Re-Dox):-

Is a type of titration based on a redox reaction between the analyte and titrant. Redox
titration may involve the use of a redox indicator.A titration characterized by the transfer
of electrons from one substance to another (from the reductant to the oxidant) with the
end point determined calorimetrically or potentiometrically or by titration.
A redox indicator (also called an oxidation-reduction indicator) is an indicator that
undergoes a definite color change at a specific electrode potential.
The requirement for fast and reversible color change means that the oxidation-
reduction equilibrium for redox indicator system needs to be established very fast.
Therefore only a few classes of organic redox systems can be used for indicator
purposes.There are two common types of redox indicators:

 metal-organic complexes (Ex. phenanthroline)

 true organic redox systems (Ex. Methylene blue)
Sometimes colored inorganic oxidants or reductants (Ex. Potassium manganate
, Potassium dichromate) are also incorrectly called redox indicators.
Almost all redox indicators with true organic redox systems involve a proton as a
participant in their electrochemical reaction.
Experiment No.(19):-Determination of the Dissolved Oxygen (D.O) in
water by iodometric method (winkler method)
Theory:-The Winkler Method is a technique used to measure dissolved oxygen in
fresh water systems. Dissolved oxygen is used as an indicator of the health of a water
body, where higher dissolved oxygen concentrations are correlated with high
productivity and little pollution Dissolved oxygen analysis can be used to determine:
• the health or cleanliness of a lake or stream,
• the amount and type of biomass a fresh water system can support,
• the amount of decomposition occurring in the lake or stream.
The Winkler test is used to determine the concentration of dissolved oxygen in water
samples An excess of manganese(II) salt, and hydroxide (OH–) ions is added to a
2
water sample, then oxygen in water react with Mn + oxidized by the dissolved oxygen
in the water sample into a brown manganese precipitate:-

4Mn2+ + O2 + 8OH- + 2H2O 4Mn(OH)3

‫ينب بسار‬
The second part of the Winkler test reduces (acidifies) the solution. The precipitate
will dissolve back into solution. The acid facilitates the conversion by the brown,
Manganese-containing precipitate of the Iodide ion into elemental Iodine.
2Mn(OH)3(S) + 3H2SO4 2Mn3+ + 3SO42- + 6H2O

2Mn3+ + 2I- 2Mn2+ + I2

Iodide Iodine

Thiosulfate is used, with a starch indicator, to titrate the iodine.

2NaS2O3 + I2 starch
Na2S4O6 + 2NaI
 The number of moles of iodine produced= the number of moles of dissolved oxygen
in freshwater.
Procedure:-A-Reagents:-

1. Manganous sulfate solution: Dissolve 12 g MnSO4⋅4H2O, 10g MnSO4⋅2H2O,

or 9.1 g MnSO4⋅H2O in distilled water, filter, and dilute to 25 ml.
2. Alkali-iodide reagent:
Dissolve 12.5 g NaOH (or 17.5 g KOH) and 3.375 g NaI (or 3.75g KI) in distilled
water and dilute to 25 ml.
3. Sulfuric acid, H2SO4, conc.
4. Starch indicator: dissolve 0.2 gm from it in 200 ml D.W.
5. Standard sodium thiosulfate titrant (0.025 N): Dissolve 0.155 g Na2S2O3⋅5H2O
in 25 ml distilled water.
B-The work:-

1. To the sample collected in a 250- to 300-mL bottle, add 2 mL MnSO4

solution, followed by 2 mL alkali-iodide reagent. Stopper and mix by inverting
bottle a few times. When precipitate has settled sufficiently (to approximately
half the bottle volume) to leave clear supernatant above the manganese
hydroxide floc, add 2.0 mL conc H2SO4. Restopper and mix by inverting several
times until dissolution is complete.
2. Titrate a volume corresponding to 200 mL original sample after correction
for sample loss by displacement with reagents. Thus, for a total of 4 mL (2 mL
each) of MnSO4 and alkali-iodide reagents in a 300-mL bottle, titrate
200×300/(300 - 4) = 203 mL.

3. Add a few drops of starch solution and Titrate with 0.025M Na2S2O3⋅5H2O
solution; continue titration to first disappearance of blue color.
Calculations:-Calculate the conc. of D.O by ppm:-

DO as mg / L = ml of Na2S2O3.5H2O × 2

Discussion:-
1. What is the Winkler Method?
2. What are the redox indicators?
3. What is the Dissolved oxygen?
4. What the advantage is of applied this experiment?

4
 Experiment No.(20):-Determination of available chloride in
hypochlorite
Theory:-Most hypochlorite's are normally obtained only in solution, but calcium
hypochlorite exists in the solid form in commercial bleaching powder which consists
essentially of a mixture of calcium hypochlorite Ca(OC1)2 and the basic chloride
CaC12,Ca(OH)2,H2O; some free slaked lime is usually present. The active constituent
is the hypochlorite, which is responsible for the bleaching action. Upon treating
bleaching powder with hydrochloric acid, chlorine is liberated: OCl - + Cl- + 2H+ =
C12 + H2O
The available chlorine refers to the chlorine liberated by the action of dilute acids on
the hypochlorite, and is expressed as the percentage by weight in the case of bleaching
powder. Commercial bleaching powder contains 36-38 per cent of available chlorine.
Two methods are in common use for the determination of the available chlorine. In the
first, the hypochlorite solution or suspension is treated with an excess of a solution of
potassium iodide, and strongly acidified with acetic acid:

OC1- + 21- + 2H+ = Cl- + 12 + H2O

The liberated iodine is titrated with standard sodium thiosulphate solution. The
solution should not be strongly acidified with acetic acid, for the little calcium chlorate
which is usually present, by virtue of the decomposition of the hypochlorite, will react
slowly with the potassium iodide and liberate iodine:

C1O- + 61- + 6H+ = C1- +312+3H2O

In the second method, the hypochlorite solution or suspension is titrated against
standard sodium arsenite solution; this is best done by adding an excess of the arsenite
solution and then back-titrating with standard iodine solution.

Procedure:- (iodometric method):-

1. Weigh out accurately about 5.0 g of the bleaching powder into a clean glass
mortar. Add a little water, and rub the mixture to a smooth paste. Add a little more
water, titration with the pestle, allow the mixture to settle, and pour off the milky
liquid into a 500 mL graduated flask.

2. Grind the residue with a little more water, and repeat the operation until the
whole of the sample has been transferred to the flask either in solution or in a state of
very fine suspension, and the mortar washed quite clean.
3. The flask is then filled to the mark with distilled water, well shaken, and 50.0
mL of the turbid liquid immediately withdrawn with a pipette. This is transferred to a
250 mL conical flask, 25 mL of water added, followed by 2 g of iodate-free potassium
iodide (or 20 mL of a 10 per cent solution) and 10 mL of glacial acetic acid.

4. Titrate the liberated iodine with standard 0.1M sodium thiosulphate solution.

Calculation:-

meq Cl2 = meq Na2S2O3

Wt.
* 1000 = N * V
At. Wt.

Wt. Cl2
% Cl2 = * 100
Wt. sample

Discussion:-

1. What is the indicator used, why?

2. Write balance equations for the titration reaction?
3. What is the suspension solution, what is differing from colloidal solution?
Experiment No.(21):- Preparation and standardization of 0.1 M
Na2S2O3 .5H2O
Theory:-The oxidation reduction reactions which involve the use of iodine may be
divided into two classes as follows:
a- Iodimetry (direct method): is the use of I2 as standard oxidizing agent for direct
determination of reducing agent (e.g. S2O32-, Sn2+, ……etc).
b- Iodometry (indirect method): is the use of I- for indirect determination of oxidizing
agent (e.g. IO3-, Cr2O72-, MnO4-, H2O2 …….etc). By addition of known excess of I-
where oxidizing agent oxidizes iodide and liberating equivalent amount of iodine
which is titrated with standard solution of thiosulphate.
Iodometry, also known as iodometric titration, is a method of volumetric chemical
analysis, a redox titration where the appearance or disappearance of
elementary iodine indicates the end point.
Sodium thiosulfate Na2S2O3•5H2O, although sodium thiosulfate (Na2S2O3·5H2O,
FW=248.17) can be obtained in high purity, solutions may exhibit some
decomposition reactions. Therefore, it is prudent to prepare solutions approximately,
and then standardize them with a primary standard reagent.
Directions here are for standardization with KIO3 (Eq. Wt.=214.02/ 6). The KIO3

6
reacts with excess KI to produce I2, as shown in the equation below:

IO3− + 5 I– + 6 H3 O+ → 3 I2 + 9 H2 O
And titrate with the Na2S2O3 solution with starch indicator until the color change from
blue to colorless. I2 + 2 S2O32− → S4 O62- + 2 I-
The principal reaction is the reduction of iodine to iodide by thiosulfate, it is called
iodometric titration.

Procedure:-
1. Boil 250 ml of distilled H2O for several minutes, and then cool, for killing
bacteria.
2. Weigh 5 gm Na2S2O3•5H2O, add to 200 ml the boiled water. 0.5 gm Na2CO3
and store the solution in the dark a bottle, This solution will not be stable for more
than one week.
3. Weigh out approximately 0.15 g KIO3. Quantitatively transfer to a 300-mL
volumetric flask and dilute with 50 ml D.W., add 2 g KI and 10 mL of (1M HCl)
4. Fill the burette with Na2S2O3 solution and slowly titrate until the solution is pale
yellow. At this point, add 3-5 mL of starch solution and continue adding titrant
dropwise until the blue dark color just disappears.

5. Repeat step4 three times.

Calculations:-

m eq Na2S2O3 = m eq KIO3

(N * V)Na2S2O3 = (N * Vburette)KIO3
Wt. of Na2S2O3
1000 * = (N * V) KIO3
Eq.Wt

Wt.
% Na2S2O3 = * 100
Wt. of sample

Discussion:-
1. Why is sodium carbonate used in the preparation of the sodium thiosulfate
solution?
2. What is the Iodometry?
3. Why is Boiling water before using it?
4. Is sodium thiosulfate primary standard solution? Why?
5. What is the difference between Iodimetry and Iodometry?
6. What is the difference between redox agent and oxidant agent?

Experiment No.(22):- Determination of vitamin C in the tablet and juice

Theory:-Vitamin C (ascorbic acid or its sodium salt) is naturally present in fresh fruit
juices or vegetables. It is also used in some pharmaceutical products. The food
industry makes use of vitamin C as an anti-oxidation additive in cooked pork meats or
canned products to avoid oxygen action.Vitamin C (ascorbic acid) has received much
attention lately, as a result of claims that it can cure various diseases, ranging from the
common cold to cancer. It is known that vitamin C is an antioxidant and is required for
connective tissue synthesis. It is also used for treatment of rheumatoid arthritis.
Vitamin C is readily oxidized by iodine in an acidic solution:
O
O
O
HO O
O + I2 + 2H+ + 2I-
H
H
O CHOH
HO CHOH
CH2OH
CH2OH

L-ascorbic acid L-dehydroxyascorbic acid

Rather than titrating directly with iodine, a known excess of iodine will be generated
directly in the solution with the ascorbic acid, according to the following reaction:

IO3- + 5I- + 6H+ → 3I2 + 3H2 O

The excess iodine which did not react with the ascorbic acid will then be back-titrated
with standard sodium thiosulfate solution: 2S2O32- + I2 → S4 O62- + 2I-
Iodine forms a complex with starch which is dark blue and the endpoint of the titration
can be detected by the disappearance of this color. By knowing the total quantity of
iodine formed, and the quantity left after reaction with vitamin C, the amount of iodine
reacted with the vitamin C can be calculated.
Procedure:-A-Determination of vitamin C in the tablet:-
1. Weigh a vitamin C tablet and grind to a powder with a mortar and pestle.
2. Dissolve the powder in 10-20 mL (0.6M H2SO4) and carefully transfer to a 500-
 mL volumetric flask. Dilute to the mark with distilled water. This is your stock
solution.
3. Pipette 10 mL of the stock solution into a conical flask and carefully add about
0.1 g of oxalic acid.
WARNING: Oxalic acid is toxic. Handle it with care, and wash your hands after
finishing the experiment.
4. Into this conical flask, pipet 25 mL of the KIO3 solution, and add about 2 g of KI
and 10 mL of (0.6M H2SO4).
5. Perform triplicate titrations with Na2S2O3 solution as before, adding 2 mL of starch
solution just prior to the endpoint. Record the volume of titrant used.

B- Determination of vitamin C in the juice:-

1. Use a graduated pipet to measure out 5 ml of juice.
2. Transfer the juice to a clean 125 ml conical flask. Add the following: 50 mL
distilled water, 5-10 mL ( 0.6M H2SO4)
3. Pipette 10 mL of the juice into a conical flask and carefully add about 0.1 g
of oxalic acid.
4. Into this conical flask, pipet 25 mL of the KIO3 solution, and add about 2 g of
KI and 10 mL of (0.6-M H2SO4).
5. Perform triplicate titrations with Na2S2O3 solution as before, adding 2 mL of
starch solution just prior to the endpoint. Record the volume of titrant used.
Calculations:-A-Calculate the normality of vitamin C in tablet:-

(N *V )vitamin C = ( N *V) Na2S2O3

1000 * Wt. of tablet

= 0.03 *V burate
Eq.Wt of vitamine C

B- Calculate the molarity of vitamin C in orange juice:-

(N *V )vitamin C = ( N *V) Na2S2O3

N*5 = 0.03 *V burate

Discussion:-

1. What is back-titration?
2. What is the L-ascorbic acid?

3. Why do you add oxalic acid to the stock solution of the vitamin C?
 Experiment No.(23):-Iiodometric determination of copper in copper
sulfate
Theory:- Pure copper is used as a primary standard for sodium thiosulfate and is
recommended when the thiosulfate is to be used for the determination of copper. Upon
addition of excess iodide to a solution of Cu (II), a precipitate of CuI is formed along
with I2. The liberated iodine is then titrated with standard sodium thiosulfate.

2 Cu2+ + 4 I- 2 CuI(s) + I2

I2 + 2 S2 O3-2 2 I- + S4O6-2
Procedure:-
1. Weigh 0.6 gm CuSO4. 5H2O.
2. Dissolve in 25 ml D.W.
3. Added 2 ml (5N HCl)
4. Transfer the solution to the conical flask capacity 300 ml and add 75 ml D.W.
5. Add a 5 ml of starch solution and Titrate with 0.025M Na2S2O3⋅5H2O solution,
continue titration to first disappearance of blue color
6. Add 1 gm NH4SCN or KSCN. Mix well; if the blue color return again, adds
another amount from sodium thiosulphate till the white precipitate is appear.
7. Repeat step 7 and 8 three time.
Calculations:-Calculate the Rate percentages for Cu in salt:-

m eq CuSO4 = m eq Na2S2O3
(N * V) CuSO4 = (N * V) Na2S2O3
Wt. of Cu in salt
1000 * = (N *V )Na2S2O3
eq.Wt

Wt Cu in CuSO4
% Cu in CuSO4 = * 100
Wt. of Sample

Discussion:- 1. Why we add KI?

2. What is the type of CuSO4 and what is deference between them?
3. Why we add KSCN?
3. Why we add HCl?

0
 Experiment No.(24):- Determination of Copper in Brass
Theory:- Brass (alloy) contains amounts of tin, lead, and zinc (and perhaps minor
amount of nickel and iron). The method is relatively simple and applicable to brasses
with less than 2% iron.
A weighed sample is treated with nitric acid, which causes the tin to precipitate as a
hydrated oxide of uncertain composition evaporation with sulfuric acid to the appearance
of sulfur trioxide eliminates the excess nitrate, redissolves the tin compound, and
possibly causes the formation of lead sulfate. The pH is adjusted amount of phosphoric
acid. An excess of potassium iodide is added, and the liberated iodine is titrated with
standard thiosulfate.

Procedure:-

1. If so directed, free the metal of foils by treated with an organic solvent, heat in an oven to
drive off the solvent.
2. Weight 0.1-0.3 mg sample into 250 ml conical flask, and introduce 5 ml of 6M HNO3 into
each.
3. Warm (HOOD) until solution is complete, add 10 ml of conc. H2SO4, and evaporate
(HOOD) until copious white fumes of SO3 are given off.
4. Allow the mixture to cool, cautiously add 30 ml of D.W, boil for 1-2 min, and again cool.
5. Add conc. NH3 dropwise and with thorough mixing to produce the intensely blue Cu
(NH3)4+2, the solution should smell faintly of ammonia (note).
6. Add with dropwise 3M H2SO4 until the color of the complex just disappear s , and then add
2 ml of 85% H3PO4. Cool to room temperature.
7. Treat each sample individually from this point on to minimize the air-oxidation of iodide
ion. Add 4 g of KI to the sample, and titrate with Na2S2O3 until the solution becomes pale
yellow.

8. Add 5 ml of starch indicator, and continue the titration until the blue color becomes faint.
Add 2 g of KSCN; swirl vigorously for 30 s. complete the titration, using the disappearance of
the blue starch/ I2 color as the end point.
Note: vapors should not be sniffed directly from the flask but instead should be wafted
toward the nose with a waving motion of one's hand.
 Calculation:-

mmol Cu = mmol Na2CO3

Wt. a
* 1000 = ( M * V) * b
At. Wt.
Wt.
Cu % = * 1000
Wt. sample

Discussion:-

1. Write balance chemical equation for the titration?

2. Why starch must added after solution become palled- yellow?
3. Why the chemical compound, HNO3, H3PO4, KI, Starch, KSCN and NH3 are added?
Experiment No.(25):- Determination of mercury
Theory:-The mercury is precipitated as mercury ( I) chloride and the latter is reacted
with standard potassium iodate solution:

IO3- + 2Hg2Cl2 + 6H+ + l3Cl- = IC1 + 4[HgC14]-2 + 3H2O

Thus:- K1O3 = 4Hg = 2Hg2C12
To determine the purity of a sample of mercury (II) salt, the following procedure in
which the compound is reduced with phosphorous (phosphonic) acid may be used; to
assay a sample of a mercury (I) salt, the reduction with phosphorous acid is omitted.

Procedure:-

1. Weigh out accurately about 2.5 g of finely powdered mercury (II) chloride, and
dissolve it in 100 mL of water in a graduated flask.

2. Shake well. Transfer 25.0 mL of the solution to a conical flask; add 25 mL water, 2
mL 1M hydrochloric acid, and excess of 50 per cent phosphorous (III) acid solution.

3. Stir thoroughly and allow standing for 12 hours or more. Filter the precipitated
mercury (I) chloride through a quantitative filter paper and wash the precipitate
moderately with cold water.

4. Transfer the precipitate with the filter paper quantitatively to a 250 mL reagent bottle;
add 30 mL concentrated hydrochloric acid, 20 mL water, and 5 mL carbon tetrachloride
or chloroform.
5. Titrate the mixture with standard 0.025M potassium iodate in the usual manner
2HgC12 + H3PO3 + H2O = Hg2C12 + 2HC1 + H3PO4

Calculation:-

mmol Hg = mmol KIO3 * mmol Hg

mmol KIO3
Wt.
* 1000 = ( M * V) KIO3 * 4
A. Wt. 1

Discussion:-

1. Why phosphoric acid is added?

2. What is the type of indicator used?
3. What is the oxidation state of mercury?
4. Why HCl and carbon tetrachloride are added?
Experiment No.(26):- Determination Antimony in stibnite (Iodimetric
titration)
Theory:-The analysis of stibnite, a common antimony ore, is atypical application of
iodimetry and is based upon the oxidation of Sb+3 to Sb+5 :-

SbO3-3 + I2 +H2O SbO4-3 + 2I- +2H+

The position of this equilibrium is strongly dependent upon the hydrogen ion
concentration. In order to force the reaction to the right, it is common practice to carry
out the titration in the presence of an excess of sodium hydrogen carbonate, which
consumes the hydrogen ions as they form.

Procedure:-
1. Dry the unknown at 110 oC for 1h, and allow it to cool in a desiccator.
2. Weigh individual samples (note1) into 500 ml conical flask.
3. Introduce 0.3 g of KCl and 10 ml of concentrated HCl to each flask.
4. Heat the mixture (HOOD) just below boiling until only white or slightly gray
residues of SiO2 remain.
5. Add 3 g of tartaric acid to each sample and heat for an additional 10 to 15 min.
6. With swirling, add water (note2) from a pipet or burette until the volume is about 100
ml.
7. If reddish Sb2S3 form, discontinue dilution and heat further to eliminate H2S,add
more HCl if necessary.
8. Add 3 drops of ph.ph indicator, and neutralize with 6 M NaOH to the first faint pink
of the indicator.
9. Discharge the color by the dropwise addition of 6 M HCl, and then add 1 ml in
excess.
10. Introduce 4 -5 g of NaHCO3 , taking care to avoid losses of solution by spattering
during the addition.
11. Add 5 ml of starch indicator, rine down the inside of the flask, and titrate with
standard 0.05 M I2 to the first blue color that persists for 30 S.
Note1: samples should contain between 1.5 and 2 mmol of antimony, consult with the instructor
for an appropriate sample size. Weight to the nearest milligram is adequate for samples larger
than 1 g.

Note2: the slow addition of water, with efficient stirring, is essential to prevent the formation of
SbOCl.

Calculation:-

a
mmol Sb = mmol I2 * b
Wt.
a
At. Wt. * 1000 = ( M * V) * b

Wt. Sb * 100
% Sb =
Wt. sample

Discussion:-

1. How many type of redox – oxidation indicator are?

2. Calculate the equivalent weight for Na2CO3 as salt and as reducing agent?
Experiment No.(27):-Determination of iron in its ore
Theory:-Potassium dichromate can be obtained pure, it is stable up to its fusion point,
and it is therefore an excellent primary standard. Standard solutions of exactly known
concentration can be prepared by weighing out the pure dry salt and dissolving it in the
proper volume of water. Furthermore, the aqueous solutions are stable indefinitely if

4
adequately protected from evaporation. Potassium dichromate is used only in acid
solution, and is reduced rapidly at the ordinary temperature to a green chromium (III)
salt. It is not reduced by cold hydrochloric acid. Potassium dichromate is therefore of
particular value in the determination of iron in iron ores: the ore is usually dissolved in
hydrochloric acid, the iron (III) reduced to iron (II), and the solution then titrated with
standard dichromate solution: Cr2O7 -2+ 6Fe+2 +14H+ = 2Cr+3 + 6Fe+3 +7H2O

In acid solution, the reduction of potassium dichromate may be represented as:

Cr2O7 -2 + 14H+ + 6e = 2Cr+3 + 7H2O

Procedure:-

1. With metallic iron. Use iron wire of 99.9 per cent assay value (Note 1). Insert a well-
fitting rubber stopper provided with a bent delivery tube into a 500 mL conical flask and
clamp the flask in a retort stand in an inclined position, the tube being so bent as to dip
into a small beaker containing saturated sodium hydrogen carbonate solution or 20 per
cent potassium hydrogen carbonate solution (prepared from the solids) .

2. Place 100 mL 1.5 M sulphuric acid (from 92 mL water and 8 mL concentrated

sulphuric acid) in the flask,

3. And add 0.5-1 g sodium hydrogen carbonate in two portions; the carbon dioxide
produced will drive out the air. Meanwhile, weigh out accurately about 0.2 g of iron
wire, place it quickly into the flask, replace the stopper and bent tube, and warm gently
until the iron has dissolved completely. Cool the flask rapidly under a stream of cold
water, with the delivery tube still dipping into the solution in the beaker (Note 2).

4. Titrate the cooled solution immediately with the dichromate solution, using either
sodium diphenylamine sulphonate or N-phenylanthranilic acid as indicator. If the former
is selected, add 6-8 drops of the indicator, followed by 5 mL of syrupy phosphoric (V)
acid: titrate slowly with the dichromate solution, stirring well, until the pure green colour
changes to a grey-green. Then add the dichromate solution drop wise until the first tinge
of blue-violet, which remains permanent on shaking, appears. If the latter indicator is
selected, add 200 mL of 1M sulphuric acid, then 0.5 mL of the indicator; add the
dichromate solution, with shaking until the color changes from green to violet-red (Note
3): 1 mole K2Cr2O7 = 6 moles Fe
**Notes. (1) Iron wire of 99.9 per cent purity is available commercially and is a suitable analytical
standard. If the wire exhibits any sign of rust, it should be drawn between two pieces of fine
emery cloth, and the n wiped with a clean; dry cloth before use.
(2) As the flask cools, the hydrogen carbonate solution is automatically drawn in until the
pressure of the carbon dioxide inside the flask is equal to the atmospheric pressure.
(3) The standardization may also be effected with ethylenediammonium iron (II) sulphate.

Calculation:-

mmol K2Cr2O7 = mmol Fe * mole K2Cr2O7

mole Fe
Wt. *1
M*V =
A. Wt. 6

Wt. Fe
% Fe in ore = * 100
Wt. of sample

Discussion:-

1. Why H2SO4 is added?

2. Why NaHCO3 or KHCO3 is added?
3. In which medium K2Cr2O7 is used and why?
4. Why K2Cr2O7 is considered primary standard material?
Experiment No.(28):-Determination of Chemical Oxygen Demand
Theory:- One very important application of potassium dichromate is in a back-titration
for the environmental determination of the amount of oxygen required to oxidize all the
organic material in a sample of impure water, such as sewage effluent. This is known as
the chemical oxygen demand (C.O.D.) and is expressed in terms of milligrams of oxygen
required per litter of water, mg L-1 . The analysis of the impure water sample is carried
out in parallel with a blank determination on pure, double-distilled water.

Procedure:-

1. Place a 50 mL volume of the water sample in a 250 mL conical flask with a ground-
glass neck which can be fitted with a water condenser for refluxing.

2. Add 1 g of mercury (II) sulphate, followed by 80mL of a silver sulphate/sulphuric acid

solution (Note 1).
3. Then add 10 mL of approximately 0.00833M standard potassium dichromate solution
(Note 2).
4. Fit the flask with the reflux condenser and boil the mixture for 15 minutes. On
cooling rinse the inside of the condenser with 50 mL of water into the flask contents.

6
5. Add either diphenylamine indicator (1 mL) or ferroin indicator and titrate with
0.025M ammonium iron (II) sulphate solution (Note 3). Diphenylamine gives a color
changes from blue to green at the end-point, whilst that for ferroin is blue-green to red-
brown. Call this titration A mL.
6. Repeat the back-titration for the blank(Titration B mL). The difference between the
two values is the amount of potassium dichromate used up in the oxidation.
Calculation:-The C.O.D. is calculated from the relationship:

C.O.D. = (A-B) X 0.2 X 20 mgL-1

As a 1 mL difference between the titrations corresponds to 0.2mg of oxygen required by
the 50 mL sample (a correction must, of course, be made if solutions of slightly different
molarities are employed); see Note 4.
**Notes. (1) This solution is prepared by dissolving 5 g of silve r sulphate in 500 mL of
concentrated sulphuric acid.

(2) The required concentration is obtained by weighing out 1.225 g of potassium dichromate and
diluting to 500 mL with de-ionized water in a graduated flask.

(3) Dissolve 4.9 g of ammonium iron (II) s ulphate heptahydrate in 150 mL of water and add 2.5
mL of concentrated sulphuric acid. Dilute the solution to 500 mL in a graduated flask.

(4) This method gives high results with samples possessing high chloride content due to reaction
between the mercury (II) sulphate and the chloride ions. In these cases the proble m can be
overcome by following a procedure using chromium(III) potassium sulphate, Cr(III)
K(SO4 )2 .12H2 O.

Discussion:-

1. What is the C.O.D?

2. What is the back titration?
3. Why HgSO4 and Ag2SO4 are added?
4. What is the Potassium dichromate color and what difference to K2CrO4?
Experiment No.(29):- Standardization of cerium(IV) sulphate solutions
Method A:-Standardization with arsenic (III) oxide:-

Theory:-Cerium (IV) sulphate is a powerful oxidizing agent; the most trustworthy

method for standardizing cerium (IV) sulphate solutions is with pure arsenic (III) oxide.
The reaction between cerium (IV) sulphate solution and arsenic (III) oxide is very slow
at the ambient temperature; it is necessary to add a trace of osmium tetroxide as catalyst.
The arsenic(III) oxide is dissolved in sodium hydroxide solution, the solution acidified
with dilute sulphuric acid, and after adding 2 drops of an ‘osmic acid’ solution prepared
by dissolving 0.1 g osmium tetroxide in 40 mL of 0.05M sulphuric acid, and the
indicator (1-2 drops ferroin or 0.5 mL N-phenylanthranilic acid), it is titrated with the
cerium(IV) sulphate solution to the first sharp color change: orange-red to very pale blue
or yellowish-green to purple respectively.

2Ce+4 + H3AsO3 + H2O = 2Ce+3 +H3AsO4 + 2H+

Procedure:-
1. Weigh out accurately about 0.1 g of arsenic (III) oxide, previously dried at 105-110°C
for 1-2 hours, and transfer to a 300mL beaker or to a 300 mL conical flask.
2. Add 10 mL of approx. 2M sodium hydroxide solution, and warm the mixture gently
until the arsenic (III) oxide has completely dissolved.
3. Cool to room temperature, and add 50 mL water, followed by 12.5 mL 2.5M
sulphuric acid.
4. Then add 3 drops 0.01 M osmium tetroxide solution (0.25 g osmium tetroxide (care!
fume cupboard) dissolved in 100 mL 0.05M sulphuric acid) and 0.5 mL N-
phenylanthranilic acid indicator (or 1-2 drops of ferroin).
5. Titrate with the 0.1 M cerium (IV) sulphate solution until the first sharp color change
occurs.
6. Repeat with two other samples of approximately equal weight of arsenic ( III) oxide.
Calculation:-Calculate the molarity of Ce+4:-

mmol Ce+4 = mmol H3AsO3 * 2

Wt.
M*V=( * 1000 )* 2
M.Wt.

Method-B:-Standardization with sodium oxalate:-

Theory:-Standardization may also be carried out with sodium oxalate; in this case, an
indirect procedure must be used as the redox indicators are themselves oxidized at the
elevated temperatures which are necessary. The procedure, therefore, is to add an excess
of the cerium (IV) solution, and then, after cooling, the excess is determined by back-
titration with an iron(II) solution. It is possible to carry out a direct titration of the
sodium oxalate if a potentiometric procedure is used.

Procedure:-A:-Potentiometric method:-
Prepare an approximately 0.1 M solution of ammonium iron(II) sulphate in dilute
sulphuric acid and titrate with the cerium(IV) sulphate solution using ferroin indicator.
B-Titrimetric method:-

1. Weigh out accurately about 0.2 g sodium oxalate into a 250 mL conical flask and add
25-30mL 1M sulphuric acid.

2. Heat the solution to about 60°C and then add about 30 mL of the cerium(IV) solution
to be standardized drop wise, adding the solution as rapidly as possible consistent with
drop formation.

3. Re-heat the solution to 60 °C, and then add a further 10 mL of the cerium(IV)
solution. Allow to stand for three minutes, then cool and back-titrate the excess cerium
(IV) with the iron (II) solution using ferroin as indicator.

4. Practically all the determinations described under potassium permanganate and

potassium dichromate may be carried out with cerium (IV) sulphate. Use is made of the
various indicators already detailed and also, in some cases where great accuracy is not
required, of the pale yellow color produced by the cerium (IV) sulphate itself. Only a few
determinations will, therefore, be considered in some detail.

Calculation:-

A: m Eq Ce+4 = m Eq Fe+2

N * V = N* V
B: m Eq Na2C2O4 = m Eq Ce +4 - m Eq Fe+2

Wt.
* 1000 =(N * V) - ( N * V)
Eq. Wt

Discussion:-

1. Why H2SO4 is added?

2. Why must heat the solution rather than cooled?
3. The solution of Ce +4 must be standardized why?
4. What is the chemical name and molecular formula of ferion indicator?
Experiment No.(30):-Determination of nitrites
Theory:- Satisfactory results are obtained by adding the nitrite solution to excess of
standard 0.1 M cerium (IV) sulphate, and determining the excess of cerium (IV) sulphate
with a standard iron(II) solution: 2Ce+4 + NO2- + H2O = 2Ce+3 + NO3- + 2H+
For practice, determine the percentage of NO in potassium nitrite, or the purity of
sodium nitrite, preferably of analytical-grade quality.

Procedure:-

1. Weigh out accurately about 1.5 g of sodium nitrite and dissolve it in 500 mL of boiled-
out water in a graduated flask.
2. Shake thoroughly. Place 50 mL of standard 0.1M cerium (IV) sulphate in a conical
flask, and add l0 mL of 2M sulphuric acid.
3. Transfer 25 mL of the nitrite solution to this flask by means of a pipette, and keep the
tip of the pipette below the surface of the liquid during the addition.
4. Allow to stand for 5 minutes, and titrate the excess of cerium (IV) sulphate with
standard 0.1M ammonium iron (II) sulphate, using ferroin or N-phenylanthranilic acid as
indicator.

5. Repeat the titration with two further portions of the nitrite solution.
6. Standardize the iron solution by titrating 25 mL of it with the cerium(IV) solution in
the presence of dilute sulphuric acid.
7. Determine the volume of the standard cerium (IV) sulphate solution which has reacted
with the nitrite solution, and there from calculate the purity of the sodium nitrite
employed.
**Note. Cerium (IV) sulphate may also be used for the following analyses.

Hydrogen pe roxide . The diluted solution, which may contain nitric or hydrochloric acid in any
concentration between 0.5 and 3M or sulphuric acid in the concentration range 0.25 to 1.5M, is
titrated directly with standard cerium (IV) sulphate solution, using ferroin or N-phenylanthranilic
acid as indicator. The reaction is: 2Ce +4 + H2 O2 = 2Ce +3 + O2 + 2H+

Persuiphate (peroxydisuiphate,). Persulphate cannot be determined directly by re duction with

iron (II) because the reaction is too slow: S2 O8 -2 + 2Fe2+ =2SO4 -2 + 2Fe +3

An excess of a standard solution of iron (II) must therefore be added and the excess back-titrated
with standard cerium (IV) sulphate solution. Erratic results are obtained, depending upon the
exact experimental conditions, because of induced reactions leading to oxidation by air of iron (II)
ion or to decomposition of the persulphate; these induced reactions are inhibited by bromide ion
in concentrations not exceeding 1 M and, under these conditions, the determination may be
carried out in the presence of organic matter.

To 25.0 mL of 0.01-0.015M persulphate solution in a 150 mL conical flask, add 7 mE of 5M

sodium bromide solution and 2 mL of 3M sulphuric acid. Stopper the flask. Swirl the contents,
then add excess of 0.05M ammonium iron (II) sulphate (15.0 mL), and allow standing for 20
minutes. Add 1 ml of 0.001 M ferroin indicator, and titrate the excess of Fe +2 ion with 0.02M
cerium(IV) s ulphate in 0.5 M sulphuric acid to the first colour change from orange to yellow.

Hexacyanoferrate(II). This can be determined by titration in 1M H2 SO4 using N-

phenylanthranilic acid.

0
 Calculation:-

m Eq NaNO3 = m Eq Ce+4 - m Eq Fe+2

Wt.
* 1000 = (N * V) - ( N* V)
Eq. Wt.

Wt. of NaNO3
purityvNaNO3 = *100
Wt. of sample

Discussion:-

1. Why boiled the solution?

2. What is the kind of ferion indicator?
3. The titration must be taken in H2SO4 medium, why?
Experiment No.(31):- Determination of iron (Fe +2)
Theory:-Permanganate ion is strong oxidation reagent, half – reaction for the
permanganate is:

MnO4- + 8H+ + 5e Mn2+ +4H2O EO= 1.51V

Permanganate solution decomposes slowly and thus require occasional restandardization.

Aqueous solution of permanganate is not stable because the ion tends to oxidize water:

4MnO4- +2H2O 4MnO2 +3O2 +4OH-

The reaction between iron and permanganate performed in acidic medium:

MnO4- + 5Fe2+ + 8 H+ Mn2+ +5 Fe3+ +4H2O

Procedure:-

A-Prepare 0.1 N oxalic acid in 50 ml volumetric flask.

Wt. 1000
0.1 = *
Eq.Wt. 50
 B-Prepare ( 50 ml) 0.1 N KMNO4:-

Wt. 1000
0.1 = *
Eq.Wt. 50

Weigh 0.6 g KMnO4. Dissolve with D.W in volumetric flask capacity 50 ml. Heat the
solution for one hour, filtrate the solution with glass wool.
C- Standarazation of KMNO4 solution:-

1. Transfer 5 ml from oxalic acid , with pipette, to conical flask capacity 300 ml
2. Add 5 ml dilute sulphuric acid.
3. Heat the mixture on the water bath for 5 min.
4. Titration against KMNO4 until the faint pink color is appear.
5. Repeat step 3 three time.
6. Calculate the normality of permanganate

(N * V) KMNO4 = (N * V )H2C2O4

N* V = 0.1 *5

D-Determination of FeSO4 solution:-

1. Transfer 10 ml from FeSO4.

2. add 5 ml dilute sulphuric acid,
3. Titration against KMNO4 until the faint pink color is appear
4. Repeat this step three times.
5. Calculate the normality of FeSO4:-

(N * V) KMNO4 = (N * V )FeSO4

N* V = ? *10

Discussion:-

1. Why is potassium permanganate not used as a primary standard?

2. Not use indicator why?
3. Added sulphuric acid why?
4. Heat and filtrate the mixture why?
5. Why is the color of solution change from colorless to pink?
6. What equivalent weight of KMNO4 in acidic, basic and neutral medium?
Experiment No.(32):- Determination phenol by Bromination
Theory:-The phenol content of wastewaters from manufacturing processes is
conveniently determined by mixing the sample with a measured excess of standard
bromated followed by an excess of bromide. The bromine liberated upon acidification
reacts with the phenol:-

BrO3- + 5Br- +6H+ 3Br2 + 3H2O

C6H5OH + 3Br2 C6H2Br3OH +3H+ +3Br-

After the bromination is complete, the excess bromine is determined employing the
procedure used for the standardization.
Procedure:-
1. Transfer a sample containing between 1-1.5 mmol of phenol to 250 ml
volumetric flask, dilute to the mark with water.
2. Pipette 25 ml aliquots of the diluted sample into 250 ml conical flask, and add
25 ml aliquots of standard KBrO3 solution.
3. Add about 1 g of KBr and about 5 ml of 3 M H2SO4 to each flask. Stopper each
flask immediately after acidification to prevent the loss of Br2.mix and let stand for
about 10 min. swirl the solution until the KBr has dissolved.
4. Titrate with standard 0.05 M Na2S2O3 until the solution is pale yellow. Add 5
ml of starch indicator, and complete the titration.
Calculation:-

a
mmol phenol = mmol Na2S2O3 *
b
a
mmol phenol = (M *V)
b

Discussion:-
 1. Form which organic compound phenol to be considered?
2. Calculate the normality of 10% KBr solution?
3. Why H2SO4, KBr, KI and KBrO3 are added?

4// Complex –formation Titration:-

Most metal ions react with electron- pair donors to form coordination compounds or
complex ion.The donor species or ligand must have at least one pair of unshared
electrons available for bond formation. Water, ammonia, and halide ions are common
inorganic ligands.

M+n + nL MLn
complex
metal ligand

Ag+ + :NH3 Ag(NH3)+

The coordination number of a cation is the number of covalent bonds that a cation
tends to form with electron donor groups.Titrimetric methods based upon complex
formation.A ligand that has more than two donor group chelating agents are known.
Like EDTA (Ethylene di amine tetra acetic acid)

HOOCH2C
CH2COOH
NCH2CH2N

CH2COOH
HOOCH2C

The use of a metal ion indicator in an EDTA titration may be written as:

M-In + EDTA = M-EDTA + In

This reaction will proceed if the metal-indicator complex M-In is less stable than the
metal-EDTA complex M-EDTA. The former dissociates to a limited extent, and
during the titration the free metal ions are progressively complexed by the EDTA until
ultimately the metal is displaced from the complex M-In to leave the free indicator
(In).
The majority for EDTA titration is Eriochrome black T, This substance is sodium 1-
(1- hydroxy-2-naphthylazo) -6-nitro-2-naphthol-4-sulphonate. In strongly acidic
solutions the dye tends to polymerise to a red-brown product, and consequently the
indicator is rarely applied in titrations of solutions more acidic than pH = 6.5.

4
 Experiment No.(33):- Determination of water hardness
Theory:-Water hardness was defined in terms of the capacity of cation in the water to
replace the sodium or potassium in soaps and form sparingly soluble products.
Water hardness determined by an EDTA titration after the sample has been buffered to
pH 10. Mg, which forms the least stable EDTA complex of all of cation in water
sample, is not titrated untile enough reagent has been added to complex all of other
cation in the sample. Therefore, Mg ion indicator such as EBT, can serve as indicator
in water hardness titration. ( Indicator EBT = H3In , EDTA= H4Y).

Ca2+ + H2Y-2 CaY2- +2H+

Ca2+ +MgY2- CaY2- + Mg2+

Mg2+ + HIn2- MgIn- +H+

MgIn- +H2Y2- MgY2- +HIn2+ +H+

Red colorless colorless blue

Procedure:-

1. Dry 3 gm Na2EDTA.2H2O (Na2 H2Y. 2H2O) at 80 C0 for 2 hour, cold in dissector for
30 min.

2. Take 0. 2 gm and transfer into 50 ml volumetric flask after dissolved in 40 ml

D.W(de-ionized), stirring, and complete the volume to the market.

3. Calculate the molarity of EDTA:-

Wt. of Na2H2Y.2H2O (gm) 1000

M EDTA= *
M.wt Na2H2Y.2H2O( g/mol) 50

4. Titration: to 50 ml sample of water add 2 ml buffering solution (NH4Cl +NH4OH ,

pH=10) and 30-40 mg EBT indicator , titrate with standard 0.01 M EDTA until the color
changes from red to blue, should there be no Mg present in the sample of water it is
necessary to add 0.1 ml Mg-EDTA solution (0.1 M) before adding indicator. The total
hardness is expressed in parts of CaCO3 per million of water. (note: if the water contains
traces of interfering ions, then 4 ml of buffering solution should be added, followed by
30 mg hydroxyl ammonium chloride and then 50 mg A.R potassium cyanide before
adding the indicator.
 Calculation:-Calculate total hardness is expressed in parts of CaCO3 per million of
water:-

Wt.(gm) Wt.(gm) ppm (mg/l)

ppm(mg/ l) = * 106 = ...1
V(ml) V(ml) 106

(M * V)CaCO3 = (M * V)EDTA

Wt.(gm) * 1000
* V(sample) = (M * V) EDTA . ..2
M.Wt(CaCO3) V (ml)

Put eq. (1) in eq.( 2), we have:-

ppm(mg/l) 1
* * V(sample) = (M * V) EDTA
103 M.Wt

(M *V)EDTA * 103 * 109.09

ppm(mg/l) =
50 ml

Discussion:-
1. Why Mg-EDTA is added?
2. What is the de-ionized water?
3. What is the coordination number?
4. What is the EBT, EDTA, and ligand?
5. How many type of hardness and must be made?

Experiment No.(34):- Determination of Iron (III): direct titration

Theory:-The end point in an EDTA titration may sometimes be detected by changes in
redox potential, and hence by the use of appropriate redox indicators. An excellent
example is variamine blue (4- methoxy-4’-aminodiphenylamine), which may be
employed in the complexometric titration of iron (III). When a mixture of iron (II) and
(III) is titrated with EDTA the latter disappears first. As soon as an amount of the
complexing agent equivalent to the concentration of iron(III) has been added, Fe(III)
increases abruptly and consequently there is a sudden decrease in the redox potential; the
end point can therefore be detected either potentiometrically or with a redox indicator.

6
Procedure:-
1. Prepare the indicator solution by dissolving 1 g variamine blue in 100 mL de-ionized
water: as already pointed out, variamine blue acts as a redox indicator.
2. Pipette 25 mL iron (III) solution (0.05M) into a conical flask and dilute to 100mL with
de-ionized water.
3. Adjust the pH to 2-3; Congo red paper may be used to the first perceptible color
change.
4. Add 5 drops of the indicator solution, warm the contents of the flask to 40 °C, and
titrate with standard (0.05M) EDTA solution until the initial blue colour of the solution
turns grey just before the end point, and with the final drop of reagent changes to yellow.
This particular titration is well adapted to be carried out potentiometrically.
Calculation:-

mmol Fe+3 = mmol EDTA

(M * V)Fe+3 = (M * V)EDTA

P Fe+3 = - Log [Fe+3]

Discussion:-
1. What is the type indicator used?
2. How many donated electron in EDTA molecule?
3. Write chemical equations to express reaction the titration?
4. What is the chemical name of EDTA and it is acidic formula?

Experiment No.(35):-Determination of nickel in presence of iron : analysis

of nickel steel
Theory:-Nickel may be determined in the presence of a large excess of iron (III) in
weakly acidic solution by adding EDTA and triethanolamine; the intense brown
precipitate dissolves upon the addition of aqueous sodium hydroxide to yield a colorless
solution. The iron (III) is present as the triethanolamine complex and only the nickel is
complexed by the EDTA. The excess of EDTA is back-titrated with standard calcium
chloride solution in the presence of thymolphthalexone indicator. The color change is
from colorless or very pale blue to an intense blue. The nickel-EDTA complex has a faint
blue color; the solution should contain less than 35 mg of nickel per 100 mL.
In the back-titration small amounts of copper and zinc and trace amounts of manganese
are quantitatively displaced from the EDTA and are complexed by the triethanolamine:
small quantities of cobalt are converted into a triethanolamine complex during the
titration. Relatively high concentrations of copper can be masked in the alkaline medium
by the addition of thioglycollic acid until colorless. Manganese, if present in quantities of
more than 1 mg, may be oxidized by air and forms a manganese (III)-triethanolamine
complex, which is intensely green in color; this does not occur if a little
hydroxylammonium chloride solution is added.
Procedure:-
1. Prepare a standard calcium chloride solution (0.01M) by dissolving 1.000 g of calcium
carbonate in the minimum volume of dilute hydrochloric acid and diluting to 1 L with
de-ionized water in a graduated flask. Also prepare a 20 per cent aqueous solution of
triethanolamine.
2. Weigh out accurately a 1.0 g sample of the nickel steel and dissolve it in the minimum
volume of concentrated hydrochloric acid (about 15 mL) to which a little concentrated
nitric acid (Ca 1 mL) has been added.
3. Dilute to 250 mL in a graduated flask. Pipette 25.0 mL of this solution into a conical
flask; add 25.0mL of 0.01M EDTA and l0mL of triethanolamine solution.
4. Introduce1 M sodium hydroxide solution, with stirring, until the pH of the solution is
11.6 (use a pH meter).
5. Dilute to about 250 mL. Add about 0.05 g of the thymolphthalexone/potassium nitrate
mixture; the solution acquires a very pale blue color.
6. Titrate with 0.01M calcium chloride solution until the color changes to an intense
blue. If it is felt that the end point color change is not sufficiently distinct, add a further
small amount of the indicator, a known volume of 0.01 M EDTA and titrate again with
0.01 M calcium chloride.
Calculation:-

mmol Ni = mmol EDTA

Wt.
( *1000 )Ni = (M * V)EDTA
A.Wt.

Wt. Ni
%Ni in Alloy = * 100
Wt. sample

Discussion:-
1. Why the EDTA does react with Ni but not with Fe+3?
2. What do you mean be the selective reaction (titration or determination)?
3. What is the type of indicator used in this titration?
4. Why CaCl2 ,HCl , and tri ethanol amine are added?
5. Write balance equation to express the titration reaction?
Experiment No.(36):-Determination of lead and tin in mixture :analysis of
solder
Theory:-A mixture of tin(IV) and lead(II) ions may be complexed by adding an excess of
standard EDTA solution, the excess EDTA being determined by titration with a standard
solution of lead nitrate; the total lead-plus-tin content of the solution is thus determined.
Sodium fluoride is then added and this displaces the EDTA from the tin (IV)-EDTA
complex; the liberated EDTA is determined by titration with a standard lead solution.
Procedure:-
1. Prepare a standard EDTA solution (0.2M), a standard lead solution (0.01 M), a 30 per
cent aqueous solution of hexamine, and a 0.2 per cent aqueous solution of xylenol
orange.
2. Dissolve a weighed amount (about 0.4 g) of solder in 10 mL of concentrated
hydrochloric acid and 2 mL of concentrated nitric acid; gentle warming is necessary.
3. Boil the solution gently for about 5 minutes to expel nitrous fumes and chlorine, and
allow cooling slightly, whereupon some lead chloride may separate.
4. Add 25.0 mL of standard 0.2M EDTA and boil for 1 minute; the lead chloride
dissolves and a clear solution is obtained. Dilute with 100 mL of de-ionized water, cool
and dilute to 250 mL in a graduated flask.
5. Without delay, pipette two or three 25.0 mL portions into separate conical flasks. To
each flask add l5mL hexamine solution, ll0 mL de-ionized water, and a few drops of
xylenol orange indicator.
6. Titrate with the standard lead nitrate solution until the color changes from yellow to
red.
7. Now add 2.0 g sodium fluoride; the solution acquires a yellow color owing to the
liberation of EDTA from its tin complex.
8. Titrate again with the standard lead nitrate solution until a permanent (i.e. stable for 1
minute) red color is obtained. Add the titrant drop wise near the end point; a temporary
pink or red color gradually reverting to yellow signals the approach of the end point.
 Calculation:-

mmol of ( Sn + Pb) = mmol EDTA- mmol Pb(NO3)2

mmol of Pb = nnol EDTA - mmol Sn

mmol of Sn = mmol of (Sn + Pb) - mmol of Pb

Wt. Pb
mmol Pb = *1000
A.Wt.
Wt. Pb
% Pb in mixture = Wt. sample *100

Wt. Sn
mmol Sn = A. Wt. *1000

Wt. Sn
% Sn in mixture = *100
Wt. sample

Discussion:-

1. Why NaF is added?

2. What displacement reaction (or titration)?
3. What is the solder? And what is contained?
4. Why is the HNO3 and HCl solution are added?
5. Why hexamine is added and xylenol organic indicator?
Experiment No.(37):-Determination of silver : indirect method
Theory:-Silver halides can be dissolved in a solution of potassium tetracyanonickelate(II)
in the presence of an ammonia—ammonium chloride buffer, and the nickel ion set free
may be titrated with standard EDTA using murexide as indicator.

2Ag + + [Ni(CN)4]+2 = 2[Ag(CN)2] - + Ni+2

It can be shown from a consideration of the overall stability constants of the ions
[Ni(CN)4]+2 (1027) and [Ag(CN)2] - (1021) that the equilibrium constant for the above
ionic reaction is 1015, i.e. the reaction proceeds practically completely to the right. An
interesting exercise is the analysis of a solid silver halide, e.g. silver chloride.

0
Procedure:-
1. Prepare the indicator by grinding 0.1 g murexide with l0g of potassium nitrate; use
about 50 mg of the mixture for each titration.
2. And an ammonium chloride solution (1 M) by dissolving 26.75 g ammonium chloride
in de-ionized water in a 500 mL graduated flask.
3. The potassium tetracyanonickelate(II) which is required to be prepared as follows.
Dissolve 25 g of analytical grade NiSO4.7H2O in 50 mL distilled water and add portion
wise, with agitation, 25g potassium cyanide. (Caution: use a fume cupboard.) A yellow
solution forms and a white precipitate of potassium sulphate separates.
4. Gradually add, with stirring, 100 mL of 95 per cent ethanol, filter off the precipitated
potassium sulphate with suction, and wash twice with 2 mL ethanol.
5. Concentrate the filtrate at ‘about 70 °C an infrared heater is convenient for this
purpose. When crystals commence to separate, stir frequently. When the crystalline mass
becomes thick (without evaporating completely to dryness), allow cooling and mixing
the crystals with 50 mL ethanol. Separate the crystals by suction filtration and wash
twice with 5 mL portions ethanol. Spread the fine yellow crystals in thin layers upon
absorbent paper, and allow standing for 2-3 days in the air, adequately protected from
dust. During this period the excess of potassium cyanide is converted into potassium
carbonate. The preparation is then ready for use; it should be kept in a stoppered bottle.

6. Treat an aqueous suspension of about 0.072 g (accurately weighed) silver chloride

with a mixture of 10 mL of concentrated ammonia solution and 10 mL of 1 M
ammonium chloride solution, then add about 0.2 g of potassium cyanonickelate and
warm gently. Dilute to 100 mL with de-ionized water, add 50 mg of the indicator
mixture and titrate with standard (0.01M) EDTA solution, adding the reagent drop wise
in the neighborhood of the end point, until the color changes from yellow to violet.

7. Palladium (II) compounds can be determined by a similar procedure, but in this case,
after addition of the cyanonickelate, excess of standard (0.01 M) EDTA solution is
added, and the excess is back-titrated with standard (0.01M) manganese (II) sulphate
solution using solochrome black indicator. Gold may be titrated similarly.

Calculation:-

mole Ag+
mmo, Ag+ = mmol EDTA *
mole EDTA
Wt.
*1000 = (M * V) * 2
A.Wt
1

Wt.
% Ag = *100
Wt. sample
Discussion:-
1. Why ethanol is added?
2. What is the yellow perception?
3. Why NH4Cl, NiSO4.7H2O, and KCN are added?
4. Write chemical equation to express the titration reaction?
Experiment No.(38):- Determination of P rotein in Bread
Theory:-This quantitative method of analysis for proteins is based on a determination
of the %w/w N in the sample. Since different cereal proteins have similar amounts of
nitrogen, the experimentally determined %w/w N is multiplied by a factor of 5.7 to give
the %w/w protein in the sample (on average there are 5.7 g of cereal protein for every
gram of nitrogen). As described here, nitrogen is determined by the Kjeldahl method.
The protein in a sample of bread is oxidized in hot concentrated H2SO4, converting the
nitrogen to NH4 +. After making the solution alkaline, converting NH4+ to NH3, the
ammonia is distilled into a flask containing a known amount of standard strong acid.
Finally, the excess strong acid is determined by a back titration with a standard strong
base titrant.
Procedure:-
1. Transfer a 2.0-g sample of bread, which has previously been air dried and ground into
a powder.
2. To a suitable digestion flask, along with 0.7 g of HgO as a catalyst, 10 g of K2SO4, and
25 mL of concentrated H2SO4. Bring the solution to a boil, and continue boiling until the
solution turns clear, and for at least an additional 30 min.
3. After cooling to below room temperature, add 200 mL of H2O and 25 mL of 4% w/v
K2S to remove the Hg2+ catalyst. Add a few Zn granules to serve as boiling stones, and
25 g of NaOH.
4. Quickly connect the flask to a distillation apparatus, and distill the NH3 into a
collecting flask containing a known amount of standardized HCl. The tip of the
condenser should be placed below the surface of the strong acid.
5. After the distillation is complete, titrate the excess strong acid with a standard solution
of NaOH, using methyl red as a visual indicator.
Calculation:-
Discussion:-
1. Oxidizing the protein converts the nitrogen to NH4+. Why is the amount of nitrogen
not determined by titrating the NH4+ with a strong base?
2. Ammonia is a volatile compound as evidenced by the strong smell of even dilute
solutions. This volatility presents a possible source of determinate error. Will this
determinate error be negative or positive?
3. Discuss the steps taken in this procedure to minimize this determinate error?
4. How does K2S remove Hg2+, and why is this important?
Experiment No.(39):- Determination of Total Chlorine Residual
Theory:-The chlorination of public water supplies results in the formation of several
chlorine-containing species, the combined concentration of which is called the total
chlorine residual. Chlorine may be present in a variety of states including free residual
chlorine, consisting of Cl2, HOCl, and OCl–, and combined chlorine residual,
consisting of NH2Cl, NHCl2, and NCl3. The total chlorine residual is determined by
using the oxidizing power of chlorine to convert I– to I3–.
The amount of I3– formed is then determined by a redox titration using S2O32– as a
titrant and starch as an indicator. Regardless of its form, the total chlorine residual is
calculated as if all the chlorine were available as Cl2, and is reported as parts per
million of Cl.
Procedure:-
1. Select a volume of sample requiring less than 20 mL of S2O32– to reach the end
point.
2. Using glacial acetic acid, acidify the sample to a pH in the range of 3 to 4.
3. Add about 1 g of KI. And titrate with Na2S2O3 until the yellow color due to I3–
begins to disappear.
4. Add 1 mL of a starch indicator solution, and continue titrating until the blue color of
the starch–I3– complex disappears. The volume of titrant needed to reach the end point
should be corrected for reagent impurities by conducting a blank titration.
Calculation:-
Discussion:-
1. Is this an example of a direct or an indirect analysis?
2. Why is the procedure not carried out directly using KI as a titrant?
3. Both oxidizing and reducing agents can interfere with this analysis. Explain what
effect each of these interferes will have on the result of an analysis?

References:-
1-Douglas A. Skooge and Donald M. West, (analytical chemistry an
introduction) ,4th edition ,NY,1986.
2- Douglas A. Skooge, Donald M. West, and F. James Holler
,(fundamental of analytical chemistry) ,5th edition,1988.
3- Douglas A. Skooge, Donald M. West, F. James Holler , and Stanly R.
Crouch ,(analytical chemistry) ,8th edition ,Brooks/Cole ,2004.
4-Gary D. Christiane, (analytical chemistry) ,6th edition ,2004.
5-David Harvy, (analytical chemistry) , 2000.
6-G. H. Jeffery, J. Bassett, J. Mendham, and R. C. Denny, (quantitative
chemical analysis) (Vogles), 5th edition, 1989.

4
 ‫ﺟﻤﮭﻮرﯾﺔ اﻟﻌﺮاق‬
‫وزارة اﻟﺘﻌﻠﯿﻢ اﻟﻌﺎﻟﻲ واﻟﺒﺤﺚ اﻟﻌﻠﻤﻲ‬
‫اﻟﺠﺎﻣﻌﺔ اﻟﻤﺴﺘﻨﺼﺮﯾﺔ‬
‫ﻛﻠﯿﺔ اﻟﻌﻠﻮم‬
‫ﻗﺴﻢ اﻟﻜﯿﻤﯿﺎء‬

‫اﻟﺘﺤﻠﯿﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ اﻟﺤﺠﻤﻲ اﻟﻌﻤﻠﻲ‬

‫ﻟﻄﻠﺒﺔ اﻟﻤﺮﺣﻠﺔ اﻻوﻟﻰ ﻛﯿﻤﯿﺎء‪ 2012 /‬م‬

‫اﻋﺪاد‬
‫اﻟﻤﺪرس اﻟﻤﺴﺎﻋﺪ‬
‫رﺑﻰ ﻓﮭﻤﻲ ﻋﺒﺎس‬
‫اﺷﺮاف‬
‫اﻟﻤﺪرس اﻟﺪﻛﺘﻮر‬ ‫اﻟﻤﺪرس اﻟﺪﻛﺘﻮر‬
‫ﻋﺒﺎس ﺷﺒﯿﺐ ﺣﺴﻦ اﻟﻜﺎظﻤﻲ‬ ‫ﻣﺤﻤﺪ ﻋﺒﺪ اﻟﮭﺎدي ﺧﻠﯿﻞ اﻟﺴﻮز‬
‫‪Method 9.1‬‬

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