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Gravimetry Calculation

Thermogravimetric analysis (TGA) measures the mass of a substance as the temperature changes. It involves heating or cooling a sample at a controlled rate while measuring its mass change over time or temperature. The sample is placed in a chamber with a balance and furnace. An example TGA curve shows mass percentage and rate of mass loss over temperature. Gravimetric analysis calculations use stoichiometric relationships and the gravimetric factor to determine the weight and percentage of analyte based on the precipitate weight. Examples show calculations for various precipitation reactions and determining identity from experimental data.

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100% found this document useful (1 vote)

4K views49 pages

Gravimetry Calculation

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MuhdLuqman

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GRAVIMETRIC ANALYSIS

• BY
• DR. RETNO ARIADI LUSIANA, M.SI
• COLLABORATION UNDIP- UMS SABAH
Thermogravimetry
TGA
DEFINITIONS
“…. a technique in which the mass of a substance is measured as a
function of temperature, while the substance is subjected to a controlled
temperature programme.”
“Controlled temperature programme” can mean:
• heating and/or cooling at a linear rate (by far commonest)
• isothermal measurements
• combinations of heating, cooling and isothermal stages
• other, more modern approaches, in which the temperature profile is
modified according to the behaviour of the sample.
INSTRUMENTATION
GAS IN BALANCE
WEIGHT
CONTROLLER

GAS-TIGHT
ENCLOSURE

SAMPLE

HEATER SAMPLE TEMP.

POWER FURNACE TEMP.

TEMPERATURE PROGRAMMER
BALANCE/FURNACE CONFIGURATIONS
EXAMPLE CURVE

Mass (%) in green, rate of mass loss (%/°C) in blue.

Unit 14
Last update : 1/5/2014 Subjects
Subjects

Steps in a Gravimetric Analysis

Example : To precipitate 10 moles of Ag+ as Ag2S, how many moles of S
2

the precipitatingagent do you need to obtain

completeprecipitation
- ?

Solution :
According to the following
precipitation reaction :
2Ag+ + S2- → Ag2S
The equivalent amount of S2- = 5 moles .
50% of the equivalent amount = 2.5 moles
So the total amount of S2- needed for complete
precipitation of Ag+ = 5 + 2.5 = 7.5 moles
Subjects

Calculations in Gravimetric Analysis

Calculation of Results from Gravimetric Data :
The results of a gravimetric analysis are generally computed from two experimental measurements :
the weight of sample and the weight of a known composition precipitate

The precipitate we weigh is usually in a different form than the analyte whose weight we wish to find.
The principles of converting the weight of one substance to that of another depend on using the
stoichiometric mole relationships.
We introduced the gravimetric factor(GF), which represents the weight of analyte per unit weight of
precipitate.

mw of analyte ( g / mole ) g analyte

GF  X R
mw of precipitate ( g / mole ) g precipitate

Where R is the number of moles of analyte in one mole of precipitate

GRAVIMETRIC Subjects
Subjects
ANALYSIS
Calculations in Gravimetric Analysis

Example : Calculate GF for the

conversions in the table on your right :
Solution : No. Analyte mw or aw precipitate mw
31
(1) G F  X 1  0.074 1 P 31 Ag3po4 419
419
174 2 K2HPO4 174 Ag3PO4 419
(2) G F  X 1  0.415
419 3 Bi2S3 514 BaSO4 233.4
514 X 1  0.734
(3) G F  4 Al 27 Al2S3 150
233.4 3
27
(4) G F  X 2  0.54
150
Subjects
Subjects

Calculations in Gravimetric Analysis

In gravimetric analysis, we are generally interested in the

percent composition by weight of the analyte in the sample,
that is

weight of analyte (g )
% analyte  X 100
weight of sample (g )

We obtain the weight of analyte from the weight of the

precipitate and the corresponding weight/mole
relationship
GRAVIMETRIC Subjects
Subjects
ANALYSIS

Calculations in Gravimetric Analysis

We i g h t of analyte ( g )  we i g ht of precipitate ( g ) X G F

We can write a general formula for calculating the percentage composition of

the analyte :
weight of precipitate (g) X GF ( g analyte / g precipitate )
% analyte  X 100
weight of sample (g)
Subjects
Subjects

Calculations in Gravimetric Analysis

Example : A 0.5962 g sample of iron ore is dissolved in perchloric acid (HClO4). All iron present is oxidized
to Fe3+. The solution is filtered to remove solid matrix materials and made basic with addition of ammonium
hydroxide. The iron precipitates as the Fe(OH)3 .xH2O gel. The precipitate is collected in a cistern crucible and
ignited to produce Fe2O3.
What is the wt. % of iron in the sample if the analysis produced 0.3210 g Fe2O3?

Solution : The overall reaction is :

2 Fe3+ + 3 OH- → Fe2O3 + 3/2 H2
From this we derive the gravimetric factor relating weight of final material to the weight of iron analyte :
Subjects

Calculations in Gravimetric Analysis

mw of analyte
gravimetric factor  X no. of moles of analyte in one mole of ppt.
mw of ppt.
55.85
 X 2  0.6995
159.69
Weight of iron  Weight of ppt. X gravimetric factor
 0.3210 X 0.6995  0.2245 g
0.2245
% iron in the ore  X 100  37.66
0.5962
Subjects

Calculations in Gravimetric Analysis

Example :
A certain barium halide exists as the hydrated salt BaX2.2H2O, where X is the
halogen. The barium content of the salt can be determined by gravimetric methods.
A sample of the halide (0.2650 g) was dissolved in water (200 mL) and excess sulfuric
acid added. The mixture was then heated and held at boiling for 45 minutes.
The precipitate (barium sulfate, mw = 233.3) was filtered off, washed and dried.
Mass of precipitate obtained = 0.2533 g. Determine the identity of X.
Calculations in Gravimetric Analysis

Solution : The precipitate is barium sulfate

1. Give the reaction formula

BaX2 BaX2.H2O + H2SO4 BaSO4 + 2HX + H2O(g)

2. determine the number of moles of barium sulfate produced, this will, in turn give us the number of
moles of barium in the original sample.

Number of moles of Ba = Wt. of BaSO4 ppt. / mw of BaSO4

= 0.2533 / 233.3 = 1.09 x 10 -3
This is the number of moles of barium present in the precipitate and, therefore, the number of
moles of barium in the original sample.
Given the formula of the halide, (i.e. it contains one barium per formula unit), this must also be
the number of moles of the halide. From this information we can deduce the relative molecular mass
of the original halide salt :
Subjects

Calculations in Gravimetric Analysis

2. determine the number of moles of the original halide salt

mw of BaCl2 . 2H2O = wt. of BaCl2.2H2O / no. of moles of Ba in BaCl2.2H2O

= 0.2650 / 1.09 X 10-3 = 244.18
Atomic wt. of Ba + 2 X mw of H2O = 137.327 + 2 X 18
= 173.327

aw of 2X = 244.18 – 173.327 = 70.85

aw of X = 70.85 / 2 = 34.43

The atomic weight ( am ) of chlorine is 35.45 which is in

good agreement with the result obtained and hence the
halide salt is hydrated arium chloride and X = Chlorine .
Subjects
Subjects

Calculations in Gravimetric Analysis

Example : You have 10 mL of 0.1 M solution of S2- and you want to precipitate S2- as
Ag2S . Calculate the volume of 0.2 M solution of Ag+ which must be added to achieve
complete precipitation ?
Solution :
2 Ag+ + S2- ↔ Ag2S
mmoles S2- = 10 X 0.1 = 1
mmoles Ag+ ( equivalent ) = mmoles S2- X 2/1 =1X 2/1= 2
mmoles Ag+ required for complete precipitation = mmoles Ag+ ( equivalent ) + 50% of 2 mmole
= 2 + 1 = 3
mmoles Ag+ = M X Vol. (mL)
3 = 0.2 X Vol. (mL)
Vol. (mL) = 3 / 0.2 = 15 mL
Subjects
Subjects

Evaluation of Gravimetric Analysis

* Gravimetric analysis, if methods are followed carefully, provides for exceedingly precise analysis.
In fact, gravimetric analysis = determine the atomic masses of many elements to six figure accuracy.

*Gravimetry provides very little room for instrumental error and does not require a series of standards for
calculation of an unknown.
*Also, methods often do not require expensive equipment.
*Gravimetric analysis, due to its high degree of accuracy, when performed correctly, can also be used to
calibrate other instruments in place of reference standards .
*However , the long time needed for the analysis makes it tedious and time consuming for this reason , the
volumetric analysis starts to overshadow gravimetry that is why we did not discuss gravimetry in more
details .
Gravimetric methods have been developed for most inorganic anions and cations, as well as for such
neutral species as water, sulfurdioxide, carbon dioxide, and iudine. A variety of organic substances can also
be easily determined gravimetrically.
Subjects
Subjects

Evaluation of Gravimetric Analysis

Examples include lactose inmilk products, salkylates in drug preparations,

phenolphthalein inlaxatives, nicotine in pesticides, cholesterol in cereals, and benz-
aldehyde in almond extracts.
Subjects
Subjects

Summary

In this unit we investigated the fundamentals of and the main steps in gravimetric
analysis .
We also discussed the optimal conditions that produce an easily filtered and pure
precipitate . The precipitating agents have been briefly studied.
The calculations of gravimetric analysis are investigated in details with help of solved
examples and tutorial exercises .
We tried to provide the student with some videos and graphs to help him understand
the main aspects of gravimetric analysis .
Tutorial

Exercise 1 : A 0.4960 g sample of a CaCO3 ( mw = 100) is dissolved in an acidic solution.

The calcium is precipitated as CaC2O4. H2O (mw = 146 ) and the dry precipitate is found to
weigh 0.6186 g. What is the percentage of CaO ( mw = 56 ) in the sample?
Your answer :
GRAVIMETRIC
ANALYSIS
Tutorial

Answer 1 :
Wt. CaO = Wt. of precipitate X ( mw of CaO / mw of CaC2O4.HO ) X 1
= 0.6186 X ( 56 / 146 ) X 1 = 0.237
% CaO = ( wt. CaO / wt. sample ) X 100 = ( 0.237 / 0.4960 ) X 100 = 47.78
GRAVIMETRIC
ANALYSIS
Tutorial
Exercise 2 : 0.8 g sample contains sulfur S ( aw = 32 ) has been dissolved . The sulfur is
precipitated as BaSO4 ( mw = 233 ) . If the weight of the precipitate is 0.3 g calculate the
percentage of sulfur in the sample ?

Your answer :