TOPIC 5: GRAVIMETRIC ANALYSIS

Traditional - Quantitative analysis

Gravimetric analysis

A+B=C

An excess of B, at unknown [ ] , is added to A so that A is completely transformed in C.

C = Obtained by weighing solid product in a pure form.
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Introduction
Gravimetric analysis is the quantitative determination of analyte through a process of precipitation/volatilization, isolation of the precipitate, and weighing the isolated product. Analyte + Reagent Precipitate pure can be filtered, well separated
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Precipitating agent

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Divided into 2: i. Precipitation gravimetry

Analyte is separated from the solution of the sample as a ppt & is converted to a compound of known composition that can be weighed. Eg: Cl- + AgNO3 AgCl + NO3-

ii. Volatilization gravimetry Analyte is separated from other constituents of a gas then serves as a measure of the analyte [ ]. Eg: NaHCO3 + H2SO4 CO2 + H2O + NaHSO4

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The ideal product should be;
very insoluble, easily filtered, and very pure and posses a known and constant composition

 Steps of a Gravimetric Analysis which require condition optimization to eliminate systematic error : Preparation of the solution Precipitation Digestion Filtration Washing Drying or Igniting Weighing Calculation

Dissolution
Sample is dried, weighed, dissolved in acid, etc.

Precipitation
Precipitation Techniques Add precipitating reagent to sample solution. Reacts with analyte to form insoluble material. Precipitate has known composition or can be converted to known composition. 2 types of Precipitating agents: Specific (react only with 1 chemical sp.) Selective (react with a limited number of sp.)

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Desirable properties of analytical precipitates: Readily filtered and purified. Low solubility, preventing losses during filtration and washing. Stable final form (unreactive). Known composition after drying or ignition.

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Ions in Solution (10-7cm) colloid Precipitate

(10-7 - 10-4cm)

(10-4cm)

During precipitation process, supersaturation occurs, followed by nucleation and precipitation. First supersaturation (soln. contains more of the dissolved salt than at equilibrium) occurs. Nucleation particles come together to produce microscopic nuclei. The the degree of supersaturation, the greater the rate of nucleation. Nucleation can be induced by scratching vessel surface, dusts, etc 10

Nucleation
Formation of nucleus or primary particles

from ion, atoms or molecules, which aggregates to form a stable second phase.

Growth of particles

on top of formed nucleus. The higher the degree of supersaturation, the higher the rate of nucleation. If rate of nucleation < rate growth of particles , big particles (crystals ) are formed (easy to filter, less impurities)
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Precipitation

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Relative supersaturation = Q-S S

Q : degree supersaturation ( [ ] Of mixed reagents before ppt) S : solubility of ppts at equilibrium

If (Q-S)/S >, small crystals (surface area) If (Q-S)/S < , larger crystals ( surface area)

Therefore, we want to keep Q and S during pptn.

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Favourable conditions for pptn

Keep Q by: Precipitate from dilute solution. Add dilute ppt reagents slowly, with stirring.
Keep S by: Precipitate from hot solution. Precipitate at as pH as possible.
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Digestion
Solution containing ppts are heated before filtering. Heating the ppts within the mother liquor (or solution from which it precipitated) for a certain period of time. Done for crystalline ppts (e.g: BaSO4) diameter >10-4cm. During digestion, small particles tend to dissolve and reprecipitate on larger ones. Trapped impurities will be dissolved. Objective: bigger and purer particles that are more easily filtered from solution. DT
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Filtering & Washing

Impurities on the surface can be removed by washing the precipitate after filtering. Water is not always a good choice. Washing with water will dilute the counter layer and the primary layer charge causes the particles to revert to the colloidal state (peptization). So we wash with an electrolyte that can be volatilized on heating (HNO3). Test for completeness of washing ~ check the presence of precipitation agent in filtrate. Impurities and excess ions are washed off the ppt in this step. 15

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Type of filter will depend on the particle size of ppts. filter paper Gooch/glass sintered crucible Colloidal ppts E.g: AgCl. Mainly small particles. Cannot be filtered using normal filtration as they are not ppt from soln. Bigger particles are not formed

Agglomeration of colloidal particles Is encouraged for formation of matter that can be easily filtered, can be ppt from solutions. Formation of larger particles

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Drying/ Igniting & Weighing

Many ppt contain varying amounts of H2O.

Adsorbed from the air (i.e. hygroscopic).

Precipitates are dried for accurate, stable mass measurements. Heating removes the solvent & any volatile sp. carried down with ppt.

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Drying/ Igniting & Weighing

Drying T depends on ppt :
AgCl : > 110 oC Al2O3 : > 1000 oC

Ignition at higher temperature is required only if a precipitate must be converted to a more suitable form for weighing. For example, Fe(HCO2)3.nH2O is ignited at 850oC for 1 hour to give Fe2O3. The compound finally weighed.

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Gravimetry Calculation
Generally express in units of gram or %. In gravimetry analysis, weight of the analyte is

given by:

weight of analyte (g) = weight of ppt (g) x GF

GF is gravimetry factor that is given by

GF =

a b

FW [analyte] FW [precipitate] a & b must be equivalent

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a = mol of analyte b = mol of ppt

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Examples of gravimetry factor (GF)

Analyte
CaO Fe3O4 Mg

ppt
CaCO3 Fe2O3 Mg2P2O7

GF
1 CaO 1 CaCO3 2 Fe3O4 3Fe2O3 2 Mg 1 Mg2P2O7

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CONTINUE
Calculate the GF Analyte K2HPO4 SiO2 P ppt Ag3PO4 K Al Si3O8 Ag3PO4

(0.4450) (0.6475) (0.0740)

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CONTINUE
A general equation for calculating the % of

analyte (A) from gravimetric data;

% Analyte = mass of analyte (g) mass of sample (g)

x 100 %

Mass analyte= Mass ppt. x Gravimetric Factor (GF)

% Analyte = mass of ppt x GF x 100 mass of sample

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Example
An ore is analyzed for the manganese content by converting the manganese to Mn3O4 & weighing it. If a 1.52g sample yields Mn3O4 weighing 0.126g, what would be the % Mn2O3 in the sample? The % Mn? (JMR: Mn= 54.94, O =16)

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Solution
%Mn2O3 = 0.126g Mn3O4 x
3 Mn2O3

2 Mn3O4

x 100%

1.52g sample = 8.58 % 3 Mn % Mn = 0.126g Mn3O4 x 1 Mn3O4 x 100%

1.52g sample = 5.97 %

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A piece of impure marble (CaCO3) is analyzed. It is found that 3.000 g of the marble react with Ba(NO3)2 solution to produce 1.25 grams of BaCO3. What % of the marble was pure CaCO3? (Fw : CaCO3 = 100, BaCO3 = 197.3) Ans: 21.1%
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Solution
CaCO3 + Ba(NO3)2 BaCO3 + Ca(NO3)2
GF = 1 mole CaCO3 1 mole BaCO3 = 0.507 = 100 g CaCO3 197. 3 g BaCO3

% CaCO3 = 0.507 x 1.25 x 100% = 21.1% 3.00 g

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Exercise
Treatment of a 0.4000 g sample of impure KCl with an excess of AgNO3 resulted in the formation of 0.7332 g of AgCl. Calculate the percentage of KCl in the sample.
(JAR: Ag = 107.9, Cl= 35.5, K= 39.1, N= 14)
Ans: 95.35%

Exercise
A sample of ore weighing 1.2504 g contains sulphur is treated with HNO3 and KClO3 to convert sulphur to BaSO4. After treating with HCL, chlorate and nitrate are removed and BaSO4 is precipitated, weighing 0.5473 g. calculate the percentage of sulphur in the sample .
(RAM S=32.064 & RMM BaSO4 = 233.40
Ans: 6.010%

Quiz
Kuiz gantian akan diadakan semasa kelas ganti khamis 24.5.2012, jam 8-10 mlm. (kuiz pd 20.5.2012 - tidak diambil dikira)