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Quantitative Analysis -
Gravimetric

• Qualitative Analysis – identification of constituents present in a sample

• Quantitative Analysis – determines the amount of the constituents present in a sample

Methods of analyses:

1- volumetric analysis – measures the volume of the solution necessary to react completely
with analyte

2- gravimetric analysis – measures the mass of a substance chemically related to the analyte

• Gravimetric Analysis

- based on the law of Definite Proportions:

states that a chemical compound always contains exactly the same proportion of elements by
mass

Law of Multiple Proportions:

states that if two elements form more than one compound between them, then the ratios of
the masses of the second element which combine with a fixed mass of the first element will be ratios of
small whole numbers.

• Example: A sample of impure sodium chloride is dissolved in water, and the chloride is
precipitated with silver nitrate (Cl- + Ag+  AgCl) furnishing 1.000 g of silver chloride. What is
the weight of chlorine in the original sample?

• Example: What weight of Fe3O4 (magnetite) will furnish 0.5430 g of Fe2O3?(hematite)

2Fe3O4 + ½ O2  3Fe2O3

Wt of Fe3O4 = 0.5430 g Fe2O3 x MW Fe3O4 x ratio

MW Fe2O3
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= 0.5430 g Fe2O3 x 231.54 g/mol Fe3O4 x 2mol Fe3O4

159.69 g/mol Fe2O3 3mol Fe2O3

= 0.5249 g Fe3O4

35.45 g/mol Cl x 1 mol Cl

143.32 g/mol AgCl 1 mol AgCl

and

231.54 g/mol Fe3O4 x 2mol Fe3O4

159.69 g/mol Fe2O3 3mol Fe2O3

can be shortened called gravimetric factor

Gravimetric factor or Chemical factor – weight of desired substance equivalent to a unit weight of given
substance

1 Cl 2 Fe3O4

1 AgCl 3 Fe2O3

• Calculation of Percentages

% constituent = wt of constituent in sample x 100

wt of sample

Example: If 2.000 g of impure sodium chloride is dissolved in water and, with an excess of silver nitrate,
4.6280 g of silver chloride is precipitated, what is the percentage of chlorine in the sample?

g Cl = 4.6280 g AgCl x 1 Cl = 4.6280 g x 35.45

1 AgCl 143.32

= 1.145 g

% Cl = wt of Cl = 1.145 x 100 = 57.25%

wt of sample 2.000

• Example: 0.5000 g sample of impure magnetite (Fe 3O4) is converted by chemical reactions to
Fe2O3 weighing 0.4110 g. What is the percentage of Fe3O4 in the magnetite?

2Fe3O4 + ½ O2  3Fe2O3
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g Fe3O4 = 0.4110 g Fe2O3 x 2 Fe3O4 =

3 Fe2O3

= 0.4110 g x 2[231.54] = 0.3973 g

3[159.69]

% Fe3O4 = 0.3973 g x 100 = 79.46%

0.5000 g

1- Calculate the gravimetric factors of the ff:

Weighed Sought Weighed Sought

a) (NH4)2PtCl6 NH3 d) B2O3 Na2B4O7.10H2O

b) MoS3 MoO3 e) (NH4)3PO4.12MoO3 P2O5

c) U3O8 U f) ZnNH4PO4 Zn2P2O7

2- What is the weight of S in 5.672 g of BaSO4?

3- A sample of ferrous ammonium sulfate containing inert material weighs 0.5013 g and
furnishes 0.0968 g of Fe2O3. what is the percentage of FeSO4(NH4)2SO4.6H2O in the sample?

4- A sample of limestone weighing 1.2456 g furnishes 0.0228 g of Fe 2O3, 1.3101 g CaSO4, and
0.0551 g Mg2P2O7. Find the percentage of a) Fe b) CaO and c) MgO in the limestone. d) What weight of
CO2 could be in combination with CaO?

5- a) What is the % composition of a brass containing only Cu, Pb and Zn if a sample weighing
0.5000 g furnishes 0.0023 g PbSO4 and 0.4108 g ZnNH4PO4? b) What weight of Zn2P2O7 is obtained by
igniting ZnNH4PO4?

• Calculations Involving A Factor weight Sample

% constituent = wt of constituent in sample x 100

wt of sample

wt of constituent = wt known x g f (unknown)

(known)

Example: The gravimetric factor of a certain analysis is 0.3427. It is desired to regulate the
weight of sample taken so that a) each centigram of the precipitate obtained will represent 1.00% of the
desired constituent, b) the percentage will be twice the number of centigrams of precipitate. What
weight of sample should be taken in each case?
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a) The relationship between the weight of precipitate and the percentage of constituent is such
that

0.01 g = 1.00% therefore

0.01 x 0.3427 x 100 = 1 x = 0.3427 g

a) 0.01 x 0.3427 x 100 = 2 x = 0.1714 g

• Calculation of the Volume of a Reagent required for a given reaction

Concentration is expressed as g solute

volume of solution

Example: How many mL of barium chloride solution containing 90.0 g of BaCl 2.2H2O per liter are
required to precipitate the sulfate as BaSO4 from 10.0 g of pure Na2SO4.10H2O?

Ba2+ + SO42-  BaSO4

1 mol BaCl2.2H2O 1 mol Na2SO4.10H2O

g BaCl2.2H2O = 10 g Na2SO4.10H2O x 1 BaCl2.2H2O

1 Na2SO4.10H2O

= 10.0 g x 244 = 7.58 g BaCl2.2H2O

322

7.58 g BaCl2.2H2O = 90.0 g BaCl2.2H2O

y (mL) 1 L x 1000mL/L

y = 84.2 mL

Example: How many mL of ammonia water of SG = 0.950 (containing 12.74% of NH 3 by mass)

are required to precipitate iron from 0.800 g of pure ferrous ammonium sulfate, FeSO 4(NH4)2SO4.6H2O,
after oxidation of the iron to ferric state?

Since, Fe3+ + 3 NH3 + 3H2O  Fe(OH)3 + 3NH4+

It follows to precipitate ferric ion: the wt of NH3

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= 0.800 g FeSO4(NH4)2SO4.6H2O x 3 NH3 .

FeSO4(NH4)2SO4.6H2O

g NH3 = 0.800 g x 3(17) = 0.1042 g

392.1

From SG of NH3 : 0.950 ≈ 0.950 g / mL solution and contains 12.74% NH3 , therefore

wt of NH3 in 1 mL solution = 0.950 x 0.1274

= 0.121 g

0.1042 g NH3 (reqd to ppt) = 0.121 g NH3

y (mL) mL solution

y = 0.861 mL

Example: How many mL of sulfuric acid (SG =1.135, 18.96% H2SO4 by mass) are required to
neutralize 75.0 mL of ammonium hydroxide (SG = 0.960, containing 9.91% NH3 by mass)

H2SO4 + 2NH3 (2NH4OH)  (NH4)2SO4 + 2HOH

mass NH3 = ρV = 0.960 g x 0.0991 x 75 mL = 7.1352g

mL

mass H2SO4 = 7.1352 g NH3 x H2SO4 (98.08)

2NH3 2(17.03)

= 20. 5467 g

Volume of H2SO4 = 20. 5467 g x 1 mL x 1 =

1.135g 0.1896

= 95. 48 mL ≈ 95.0 mL

Concentration of a reagent mixture:

Example: What weight of water must be added to 100 mL of sulfuric acid containing 26.0% by
mass H2SO4 (SG = 1.19) in order for the resulting solution to contain 12.3% H2SO4 by mass?

Mass H2SO4 initially = Vρ = 100 mL ( 1.19 g ) = 119 g

(solution)
mL
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Mass pure H2SO4 (solute) = 119 g (0.26) = 30.94 g pure

% mass = mass solute x 100

mass solution (finally)

mass solution = 30.94 + mass H2O (x)

12. 3 = 30.94 x 100

119 + x

x= 132.5447 g

Assignment:

6- a) How many mL of a solution containing 20.00 g AgNO3 per 100 mL are required to
precipitate all the Cl as AgCl from a solution containing 2.012 g of dissolved BaCl 2.2H2O? b) How many
mL of H2SO4 (SG = 1.105) are required to precipitate the Ba as BaSO4 from the same solution?

7- In the precipitation of As as MgNH4AsO4 from a solution of 0.4000 g As 2O3 that has been
oxidized to H3AsO4, it is desired to add sufficient reagent containing 64.00 g MgCl 2 per liter to precipitate
the As and also have 200 mg Mg remaining in solution. What volume is required?

8- Calculate the volume of HCl solution (SG = 1.050) required to neutralize (a) 48.6 mL of KOH
solution containing 12.0% KOH by mass (b) a solution containing 10.0 g of impure KOH (96.6% KOH, 2.2%
K2CO3, 1.2% H2O) (c) 2.00 g of Ba(OH)2.8H2O

Indirect Gravimetric Analysis:

Example: In the analysis of a 2.00 g sample of limestone, the weight of combined oxides of iron
and aluminum (Fe2O3 + Al2O3) is found to be 0.0812 g. by volumetric methods, the percentage of the
limestone of total iron calculated as FeO is found to be 1.50. What is the percentage of Al 2O3 in the
sample?

mass of FeO = 2.00 g x (1.50/100) = 0.0300 g FeO

mass of Fe2O3 = 0.0300 g FeO x Fe2O3 159.69 =

2FeO 2(71.85)

= 0.0333 g

Mass of Al2O3 = 0.0812 g – 0.0333 = 0.0479 g

% Al2O3 = 0.0479 x 100 = 2.40%

2.00
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example: In the analysis of a sample of feldspar weighing 0.4150 g, a mixture of KCl + NaCl is
obtained weighing 0.0715 g. From these chlorides, 0.1548 og of K 2PtCl6 is obtained. Calculate
percentage of Na2O in the sample.

Let x = mass of NaCl in combined chlorides

0.0715 – x = mass of KCl

mass KCl x K2PtCl6 = 0.1548

2KCl

(0.0715 – x) [ 486.01 ] = 0.1548

2(74.56)

x = 0.0240 g NaCl

mass Na2O = 0.0240 g NaCl x Na2O [ 61.98 ]

2NaCl 2(58.45)

= 0.012725 g

% Na2O = 0.012725 g x 100 = 3.066%

0.4150 g

Assignment:

9- A sample of carbonate rock weighing 1.250 g yields a precipitate of the hydrated oxides of Fe
and Al. These are filtered off and ignited. The resulting Fe 2O3 x Al2O3 is found to weigh 0.1175 g. On a
separate sample of the rock a volumetric method shows 3.22% Fe. Calculate the percentage of Al in the
rock.

10- A mixture of CaO and BaO weighs 0.6411 g and yields 1.1201 g of mixed anhydrous sulfates.
Find the percentage of Ba and Ca in the original mixture.

11- A sample of silicate weighing 0.6000 g yields 0.1803 g of NaCl + KCL. When these chlorides
are dissolved and treated with AgNO3, the resulting precipitate of AgCl is found to weigh 0.3904 g.
Calculate the percentage of Na2O and of K2O in the silicate.

12- From a sample of feldspar a mixture of KCl and NaCl is obtained that weighs 0.1506 g and
contains 55.00%Cl. What weight of K2PtCl6 could be obtained from KCl?
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