C3100 - Winter 2011

V. GRAVIMETRIC AND COMBUSTION ANALYSIS

GRAVIMETRIC ANALYSIS
(Chapter 26) Gravimetric analysis = any analysis that uses the mass of a product (precipitate) to calculate the quantity of the original analyte The precipitant (precipitating agent) can be both inorganic and organic compounds: e.g. Ag+ for Cl-, to form AgCl SO42- for Ba2+ to form BaSO4 Dimethylglyoxime (HDMG) for Ni2+ to form Ni(DMG)2 The conditions under which precipitation occurs have to be carefully controlled, and interfering species may need to be removed before analysis Very accurate measurements possible, but tedious (low throughput) Desired characteristics of a precipitate for gravimetric analysis: Pure (no co-precipitates) known composition Very low solubility (cool solution!) small KSP Easy to filter; colloids and very fine particles clog or pass through the filter High molar mass: this reduces the relative error in the mass weighed

Dr. G. Van Biesen

C3100 - Winter 2011

Precipitation and Crystal Growth Precipitation starts when the solubility of the compound has been exceeded (solution is supersaturated). The excess solute will precipitate until its concentration equals its solubility (temperature dependent). The supernatant is the solution left after the precipitate has formed. Two phases of crystal growth: Nucleation: molecules in solution come together randomly to form small aggregates (nuclei) Particle growth: nuclei grow in size by adding more molecules to form crystals, or by collision and combination of nuclei In gravimetric analysis, we want to allow particles to grow to sizable dimensions (several m) so they filter easily. Colloids (1 ~500 nm diameter) have to be avoided. Nucleation dominates in highly supersaturated solutions, and this can be avoided by: Raising the temperature: precipitate from a hot solution (increases solubility decreases supersaturation) Adding precipitant slowly, with vigorous mixing to prevent local supersaturation Using low concentrations of analyte and precipitant
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Dr. G. Van Biesen

C3100 - Winter 2011

Often, precipitates are more soluble at low pH. In that case, precipitate near the low end of the pH where precipitation is still quantitative Another reason why small particles and colloids in gravimetric analysis have to be avoided, is that they are much worse for co-precipitation of impurities (because of the larger surface area). Co-precipitation can be under the form of: adsorption: bound to the surface of the crystal absorption: inside of the crystal: Inclusions: Ions which replace analyte ions in the crystal lattice. The probability of this happening is greater if the ion has the same charge and is of similar size as the analyte ion (e.g. K+ for NH4+ in NH4MgPO4; Ba2+ for Pb2+ in PbSO4) Occlusions: Pockets of impurity trapped within the growing crystal. Occlusions are more likely during rapid growth of the crystal. They are decreased by using a digestion period (see further). Note: an example where we do want a precipitate with a large surface area is when using an adsorption indicator in a titration (e.g. Fajans)
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Precipitation in the presence of electrolytes Particles in solution are almost always charged due to adsorption of ions at their surface e.g. a colloidal AgCl particle forming in 0.1 M HNO3 (excess Ag+)
Surface of AgCl has pos. charge because of adsorption of Ag+ (in excess relative to Cl-). Adsorption of Ag+ preferred over H+ because of better size compatibility. Region of solution directly surrounding the particle = Ionic atmosphere has a net neg. charge Particle + ionic atmosphere = electric double layer moves as a unit through solution Primary layer

In order for colloidal particles to coalesce and grow, they have to collide. However, their ionic atmospheres repel one another.
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Dr. G. Van Biesen

C3100 - Winter 2011

Common solutions to this problem: Increase their kinetic energy by heating (collisions are more energetic so that electrostatic repulsion is overcome) Increase electrolyte conc., which decreases the volume (thickness) of the ionic atmosphere and allows particles to come closer together before electrostatic repulsion becomes significant After precipitation, most procedures call for a digestion period; the precipitate is left in the presence of the (hot) mother liquor. This allows for slow recrystallization and overall increase in particle size (because small particles have a higher surface energy, they dissolve easier than larger ones, and are precipitated on the larger particles), and expelling of impurities Washing of precipitates: After collection of the precipitate on the filter, it has to be washed to remove any droplets of the mother liquor. This is done by breaking the suction first, and stirring the precipitate in a minimum amount of water, or better: electrolyte solution. Water washes away the ionic atmosphere of the crystals (electrical double layer expands, increasing repulsion by the primary layer) and the product breaks up = peptization. The electrolyte used for washing has to be volatile, so it will be lost during drying of the product (e.g. dilute HNO3 and HCl, NH4Cl).
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In many procedures, after the mother liquor is washed away, the precipitate is redissolved, and then reprecipitated. During the 2nd precipitation, the concentration of impurities is lower than during the 1st precipitation, and the precipitate will be more pure. Sometimes a masking agent is added prior to precipitation to prevent precipitation of impurities. For instance, in the gravimetric analysis of Ba2+ with N-p-chlorophenylcinnamohydroxamic acid, excess KCN is added to keep Ag+, Mn2+, Zn2+ etc. in solution. Product Composition Final product must have a stable and known composition Many precipitates contain a variable quantity of water and must be dried to remove all water or give a known stoichiometry of H2O : hygroscopic water, and inclusion water: can often (but not always) be removed by drying at 110-130 C water of crystallization (e.g. in NiCl2(H2O)6) requires higher temperatures

Dr. G. Van Biesen

C3100 - Winter 2011

Ignition (strong heating) is often used to change the chemical form of some precipitates e.g. igniting Fe(HCO2)3.nH2O at 850 C gives Fe2O3 Thermogravimetric analysis can be used to find out how the composition of a precipitate changes as it is heated, and what temperature is needed to remove all water

Fig. 26.4, Harris 8th Ed.

Some gravimetric problems: Problem 1 A 11.1324 g sample of iron ore was digested in concentrated HNO3. The resulting solution was diluted with water to 250.00 mL. Three 50.00 mL portions were taken and the iron(III) was precipitated as Fe2O3xH2O by the addition of NH3(aq). After filtration and washing, the precipitate from each of the three samples was ignited at high temperature to give an average mass of 0.5394 g of pure Fe2O3. Calculate the % Fe in the ore sample. Problem 2: System with 2 unknowns A 0.4000 g sample containing only NaCl and BaCl2 yielded 0.8415 g of dried AgCl. Calculate the mass percent of each compound in the sample. Problem 3: Effect of washing on accuracy Calculate the percentage loss of Ni(DMG)2 when 250.0 mL of water is used to wash precipitates of a) 0.2578g and b) 0.08634g. Assume that the wash water becomes saturated with Ni(DMG)2 and that the solubility of Ni(DMG)2 in water is 3.5 x 10-4 g L1
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Dr. G. Van Biesen

C3100 - Winter 2011

Solution to Problem 1
nFe 2O 3 = nFe 0.5394g = 3.377 8 10 3 mol 159.69 g mol -1 2 mol Fe = 3.377 8 10 3 mol Fe 2O 3 = 6.755 6 10 3 mol Fe 1 mol Fe 2O 3

mass Fe = 6.755 6 10 3 mol Fe 55.847 g mol -1 mass Fe = 0.3772 8 g Fe (in 50 mL) mass Fe in 250 mL = 0.3772 8 g x 250.00 mL = 1.886 4 g 50.00 mL

1.8864 g Fe %Fe = 100% = 16.95% 11.1324 g ore

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Solution to Problem 2
Let x = mass of NaCl 0.4000 x = mass of BaCl2 0.8415 (g) 143.32 (g/mol) moles of NaCl = moles of BaCl2 = x (g) 58.442 (g/mol) 0.4000 (g) x (g) 208.23 (g/mol)

Moles of AgCl =

= 0.005871 mol AgCl = mol Cl-

Each mol of NaCl contributes 1 mol of Cl-, each mol of BaCl2 contributes 2 mol of Cl0.005871 mol = x (g) 58.442 (g/mol) +2 0.4000 (g) x (g) 208.23 (g/mol)

Mass of NaCl x = 0.2704 g Mass of BaCl2 = 0.4000 g 0.2704 g = 0.1296 g

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Dr. G. Van Biesen

C3100 - Winter 2011

Solution to Problem 3 loss = solubility x volume wash water loss = 3.5 x 10-4 g L1 x 0.250 L x 1000mg/1g loss = 0.086 mg (very low) a) b) %loss = 0.033% %loss = 0.10%

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Precipitation Titrations
Gravimetric analysis: add excess of precipitating reagent to analyte in solution; weigh mass of precipitate, find concentration of analyte Precipitation titration: add precipitating reagent (= titrant of known conc.) incrementally to analyte solution, monitor either [analyte] or [titrant] to locate the end point of the titration

Examples: determination of Cl-, Br-, I- and SCN-, with Ag+ as titrant determination of SO42-, with Ba2+ as titrant determination of PO43- and C2O42- with Pb2+
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Dr. G. Van Biesen

C3100 - Winter 2011

Precipitation titrations: calculating concentrations Calculate pAg+ and pBr- for the addition of 10.00 mL, 24.90 mL, 25.00 mL, and 25.10 mL of 0.1000 M Ag+ to 50.00 mL of 0.05000 M Br-. Ksp AgBr = 5.0 x 10-13 Titration reaction: Calculate Ve: Ag+ + Br AgBr(s)

#moles Br- = #moles Ag+ 50.00 mL 0.05000 M = Ve 0.1000 M Ve = 25.00 mL

Before EP: 10.00 mL Ag+ added: Ve - V [Br-] = CA Ve = 0.05000 M = 0.02500 M

Vi Vi + V 25.00 mL 10.00 mL 25.00 mL 50.00 mL 50.00 mL + 10 ml

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pBr- = 1.60 The concentration of Ag+ in equilibrium with this much Br- is: [Ag+] = Ksp [Br-] = 5.0 x 10-13 0.02500 = 2 x 10-11 M pAg+ = 10.70

24.90 mL Ag+ added: Using the same approach, we find pBr- = 3.87 and pAg+ = 8.43 Note that [Ag+] is still negligible compared to [Br-], even though the reaction is 99.6% complete 25.00 mL Ag+ added: at the EP: exactly enough Ag+ is added to react with Br-; the AgBr redissolves to give equal concentrations of Ag+ and Braccording to the Ksp: AgBr
x dissolves

Ag+ + Brx x

[Ag+][Br-] = Ksp x2 = Ksp

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Dr. G. Van Biesen

C3100 - Winter 2011

x = K sp = 5.0x10-13
x = 7.1 x 10-7 M = [Ag+] = [Br-] pAg+ and pBr = 6.20

Note that these values are independent of the original concentrations or volumes. At the EP, the problem of finding [Ag+] and [Br-] is the same as for dissolving pure AgBr in water. 25.10 mL Ag+ added: post-EP [Ag+] is determined by Ag+ added after EP, since virtually all Ag+ added before EP has precipitated. [Ag+] is determined using the excess volume of Ag+ (with original conc. [Ag+]0) , and taking into account the dilution : [Ag+] = (V Ve) [Ag+]0 Vi + V = (25.10 mL 25.00 mL) (0.1000 M) 50.00 mL + 25.10 mL This is essentially a simple dilution!

= 1.33 x 10-4 M [Br-] = Ksp [Ag+]

pAg+ = 3.88 pBr- = 8.42

= 3.76 x 10-9 M

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Factors that influence the shape of the titration curve: Concentration: Titration of I- (0.1, 0.01, 0.001 M) with Ag+ (0.05 M, 0.005 M and 0.0005 M resp.) The larger the change in p function, the sharper the endpoint Before Ve: [Ag+] = Ksp [I-]

If [I-] , then [Ag+] and pAg+ After Ve: excess [Ag+], so with [Ag+] , pAg+

Fig. 26-8, Harris 8th Ed.

Note that only when the stoichiometry of the reaction is 1:1, the EP is the steepest (middle) part of the curve. Otherwise, the EP is not an inflection point. Usually, conditions are such that the inflection point is a good estimate of the EP, regardless of the stoichiometry.
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Dr. G. Van Biesen

C3100 - Winter 2011

Solubility (effect of Ksp): 25.00 mL of 0.1000 M I, Br, and Cl All titrated with 0.0500 M Ag+ (Ve = 50.00 mL for all)

X- + Ag+

AgX(s) (X = Cl, Br, I) Ksp [X-]

Before Ve: [Ag+] =

[X-] is the same for all anions: Ve - V Vi [X-] = CA Vi + V Ve Thus [Ag+] is directly proportional to Ksp:
Fig. 26-9, Harris 8th Ed.

The smaller Ksp, the smaller [Ag+], and the larger pAg+; therefore the lower the concentration of analyte that can be analyzed by titration.
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After Ve: Notice from the figure that the part of the titration curve after Ve is independent of the anion. pAg+ is here only determined by the excess Ag+ (see earlier) Analysis of mixtures: For the analysis of mixtures, it is necessary that each ion is (nearly) quantitatively precipitated before precipitation of the next one starts. This requires that the Ksps differ by at least 4 orders of magnitude. Ksp values for ions whose precipitates have different stoichiometries cannot be used to predict the order of precipitation e.g. a mixture of CO32, Cl, and PO43 titrated with Ag+.
ion CO32 Cl PO43 precipitate Ag2CO3 AgCl Ag3PO4 Ksp expression Ksp = [Ag+]2[CO32] Ksp = [Ag+][Cl] Ksp = [Ag+]3[PO43]
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Dr. G. Van Biesen

C3100 - Winter 2011

If stoichiometries are the same: precipitate with lowest Ksp is formed first Addition of AgNO3 to a solution containing both KI and KCl
Ksp(AgCl)= 1.8 x 10-10; Ksp(AgI)= 8.3 x 10-17

When all I- has precipitated, there is an increase in [Ag+] and now AgCl will precipitate (because in the figure not all I- has completely precipitated when AgCl starts to precipitate, VEP is the end of the steep portion of the curve) Because of some co-precipitation of AgCl with AgI, VEP for AgI is slightly overestimated.

VEP if no Cl- present Fig. 26-10, Harris 8th Ed.

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Endpoint detection for precipitation reactions: Either electrodes or indicators Fajans Method: Adsorption indicator Precipitation of anions with cations: e.g. Cl with Ag+: Ag+ + Cl AgCl(s) Before EP: Excess Cl in solution. Particles of AgCl have a negative charge due to extra Cl-s adsorbed on exposed Ag+. After EP: Excess Ag+ in solution. Particles of AgCl have a positive charge due to extra Ag+s adsorbed on exposed Cl-. The indicator dichlorofluorescein is negatively charged above pH ~ 5, and adsorps quickly to the positively charged crystals produced immediately after the EP. This changes the color of the indicator (yellow pink). Precipitation of cations with anions: e.g. Hg22+ with Cl : Hg22+ + 2 Cl Hg2Cl2(s) This time, the crystals have a positive charge before the EP, and a negative charge after the EP. A cationic indicator (e.g. bromophenol blue) is now used.
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Dr. G. Van Biesen

C3100 - Winter 2011

Volhard Method: halide analysis - formation of a soluble, coloured complex at EP Backtitration: To a measured volume of sample, a solution of Fe(NO3)3 and some HNO3 are added (acidifying the sample prevents hydrolysis of Fe3+). Halide ion is quantitatively precipitated with a measured excess of standard AgNO3 solution: AgX(s) X- + Ag+ The unreacted Ag+ is then titrated with standard KSCN to AgSCN(s): AgSCN(s) Ag+ + SCNWhen all Ag+ has reacted, SCN- reacts with Fe3+ to give a red complex: [FeSCN]2+ (red) Fe3+ + SCNAbove procedure works well for Br- and I-, but a problem arises with Cl-: AgCl (Ksp = 1.8 x 10-10) is more soluble than AgSCN (Ksp = 1.0 x 10-12). AgCl(s) + SCNAgSCN(s) + Cl-

This reaction occurs especially near the EP, so that more SCN- has to be added, and the amount of Cl- is underestimated (endpoint fades).
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Therefore, the AgCl(s) formed in the first step is either filtered (and only unreacted Ag+ is titrated with SCN-), or for instance nitrobenzene or polyvinylpyrrolidone is added to the sample, which coats AgCl and prevents it from dissolving.

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Dr. G. Van Biesen

C3100 - Winter 2011

COMBUSTION ANALYSIS: Determination of C, H, N, S (and O)

Small amount of sample accurately weighed in Ag or Sn capsule (sealed) Analyzer swept with pure He, just before run, a measured excess of O2 is added to He stream Capsule dropped into preheated ceramic crucible; capsule melts and sample is instantaneously oxidized C, H, N, S
1050 C / O2

CO2(g) + H2O(g) + N2(g) + SO2(g) (+ some SO3(g))

The initial reaction products of the combustion pass through several catalysts to complete their transformation: C, CO + O2 SO3 O2 Cu Cu WO3 CO2

SO2 + CuO (s) CuO (s)

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Dynamic Flash Combustion: short burst of gaseous products, so that reaction products can be analyzed via a GC with a thermal conductivity detector (GC/TCD)

For the analysis of oxygen, the sample is thermally decomposed in the absence of oxygen (pyrolysis). Oxygen released by the sample is converted into CO, measured with a GC/TCD. 26

Dr. G. Van Biesen

C3100 - Winter 2011

Stoichiometry to the rescue (Journal of Chemical Education 1988, 65 (9), 800) In the beginning of the 20th century, industrial organic chemistry was blooming. Dye manufacturers used large vats with boiling mixtures of sulfuric and nitric acid. One day, a worker in one of those factories did not return home, and his disappearance was an absolute mystery. The manager of the factory eventually suggested that the worker had fallen into the acid, and had been dissolved, hair, flesh, bones, boots and all. In order for the wife to claim insurance money, she needed evidence of his death. The acid was analyzed for phosphorus, which is present in the human body at ~ 0.63%.
Large vat of nitric and sulfuric acid, perhaps containing one dissolved human body Take 100 mL samples and treat with molybdate reagent (NH4)3[P(Mo12O40)].12H2O spectrophotometry, redox titration, acid-base titration Heat to 400 C Gravimetric determination of P2O524MoO3 It is assumed that all P is converted to H3PO4 and that the contents of the vat is homogenous

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The gravimetric procedure yielded a mass of P2O524MoO3 (MM = 3596.46) of 0.3718 g. A blank sample of a mixture of nitric and sulfuric acid of the same volume (100 mL) gave 0.0331 g of P2O524MoO3 mass of P2O524MoO3 due to sample = 0.3718 0.0331 = 0.3387 g #moles of P = 2 x [0.3387 (g) / 3596.46 (g/mol)] = 1.884 x 10-4 mol P = 1.884 x 10-4 (mol) x 32.0 (g/mol) = 6.03 x 10-3 g P With a volume of 8000 L of acid, the total amount of P in the vat would be: 8000 (L) x 6.03 x 10-3 (g) / 0.100 (L) = 482 g P Assuming a mass of 70 kg, and with an average content of 0.63% P for the human body, the expected amount of P would be: 70 x 103 (g) x 0.0063 = 441 g P which is close to the value found (482 g). Based upon this analysis, the insurance company paid the money owed to the widow.

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Dr. G. Van Biesen