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# Problems

MOLE CONCEPT
PROBLEM 1 A crystalline hydrated salt on being rendered anhydrous, loses 45.6% of its weight. The
percentage composition of anhydrous salt is: Al = 10.5%, K = 15.1%, S = 24.8% and O = 49.6%. Find
the empirical formula of the anhydrous and crystalline salt.
PROBLEM 2 How much quantity of zinc will have to be reacted with excess of dilute HCl solution to
produce sufficient hydrogen gas for completely reacting with the oxygen obtained by decomposing
5.104 g of potassium chlorate?
PROBLEM 3 A 1.85 g sample of mixture of CuCl 2 and CuBr 2 was dissolved in water and mixed
thoroughly with 1.8 g portion of AgCl. After reaction, the solid which now contain AgCl and AgBr was
filtered, dried and weighed to be 2.052 g. What was the % by weight of CuBr 2 in the mixture?
PROBLEM 4 1.0 g of a sample containing NaCl, KCl and some inert impurity is dissolved in excess of
water and treated with excess of AgNO 3 solution. A 2.0 g precipitate of AgCl separate out. Also sample
is 23% by mass in sodium. Determine mass percentage of KCl in the sample.
PROBLEM 5 A one gram sample containing CaBr 2 , NaCl and some inert impurity was dissolved in
enough water and treated with excess of aqueous silver nitrate solution where a mixed precipitate of
AgCl and AgBr weighing 1.94 g was obtained. Precipitate was washed, dried and shaken with an
aqueous solution of NaBr where all AgCl was converted into AgBr. The new precipitate which contain
only AgBr now weighed to be 2.4 g. Determine mass percentage of CaBr 2 and NaCl in the original
sample.
PROBLEM 6 Sulphur combines with oxygen to form two oxide SO 2 and SO 3 . If 10 g of S is mixed with
12 g of O 2 , what mass of SO 2 and SO 3 will be formed, so that neither S nor oxygen will be left at the end
of reaction?
PROBLEM 7 An aqueous solution of ethanol has density 1.025 g/mL and it is 8.0 M. Determine
molality m of this solution.
PROBLEM 8 An aqueous solution of acetic acid has density 1.12 g/mL and it is 5.0 m. Determine
molarity (M).
PROBLEM 9 Octane is a component of gasoline. Incomplete combustion of octane produces some CO
along with CO 2 and H 2O, which reduces efficiency of engine. In a certain test run, 1.0 gallon of octane is
burned and total mass of CO, CO 2 and H 2O produced was found to be 11.53 kg. Calculate efficiency of
the engine, density of octane is 2.65 kg/gallon.
PROBLEM 10 The formula of a hydrated salt of barium is BaCl 2 xH 2O. If 1.936 g of this compound
gives 1.846 g of anhydrous BaSO 4 upon treatment with H 2SO 4 , calculate x.
PROBLEM 11 A mixture of CuSO 4 5H 2O and MgSO 4 7H 2O was heated until all the water was
driven-off. If 5.0 g of mixture gave 3 g of anhydrous salts, what was the percentage by mass of
CuSO 4 5H 2O in the original mixture?
PROBLEM 12 A sample of clay contain 15% moisture, and rest are CaCO 3 and non-volatile SiO 2 . This
on heating loses part of its moisture, but CaCO 3 is completely converted into CaO. The partially dried

Problems in Chemistry

sample now contain 7.35% moisture and 51.5% SiO 2 . Determine mass percentage of CaCO 3 in the
original sample.

PROBLEM 13 Chlorine dioxide (ClO 2 ), has been used as a disinfectant in air conditioning systems. It
reacts with water according to the reaction:
ClO 2 + H 2O HClO 3 + HCl
In an experiment, a 10.0 L sealed flask containing ClO 2 and some inert gas at 300 K and 1.0
atmosphere pressure is opened in a bath containing excess of water and all ClO 2 is reacted quantitatively.
The resulting solution required 200 mL 0.9 M NaOH solution for neutralization. Determine mole
fraction of ClO 2 in the flask.
PROBLEM 14 Potassium salt of benzoic acid (C 6 H 5COOK) can be made by the action of potassium
permanganate on toluene as follows:
C 6 H 5CH 3 + KMnO 4 C 6 H 5COOK + MnO 2 + KOH + H 2O
If the yield of potassium benzoate cant realistically be expected to be more than 71%, what is the
minimum number of grams of toluene needed to achieve this yield while producing 11.5 g of
C 6 H 5COOK?
PROBLEM 15 Manganese trifluoride can be prepared by the following reaction:
MnI 2 ( s) + F2 ( g ) MnF3 + IF5
What is minimum number of grams of F2 that must be used to react with 12.0 g of MnI 2 if overall
yield of MnF3 is no more than 75%.
PROBLEM 16 A compound containing Ca, C, N and S was subjected to quantitative analysis and
formula mass determination. A 0.25 g of this compound was mixed with Na 2CO 3 to convert all Ca into
0.16 g CaCO 3 . A 0.115 g sample of compound was carried through a series of reactions until all its S was
changed into SO 2
4 and precipitated as 0.344 g of BaSO 4 . A 0.712 g sample was processed to liberate all
of its N as NH 3 and 0.155 g NH 3 was obtained. The formula mass was found to be 156. Determine the
empirical and molecular formula of the compound.
PROBLEM 17 A 0.2 g sample, which is mixture of NaCl, NaBr and NaI was dissolved in water and
excess of AgNO 3 was added. The precipitate containing AgCl, AgBr and AgI was filtered, dried and
weighed to be 0.412 g. The solid was placed in water and treated with excess of NaBr, which converted
all AgCl into AgBr. The precipitate was then weighed to be 0.4881 g. It was then placed into water and
treated with excess of NaI, which converted all AgBr into AgI. The precipitate was then weighed to be
0.5868 g. What was the percentage of NaCl, NaBr and NaI in the original mixture.
PROBLEM 18 A mixture of NaI and NaCl when heated with H 2SO 4 produced same weight of Na 2SO 4
as that of original mixture. Calculate mass percentage of NaI in the original mixture.
PROBLEM 19 Ammonia is manufactured by the reaction of N 2 and H 2 . An equilibrium mixture
contains 5.0 g of each N 2 , H 2 and NH 3 . Calculate mass of N 2 and H 2 present initially and maximum
amount of NH 3 that can be produced.
PROBLEM 20 Consider the following reactions:
XeF2 + F2 XeF6
and
XeF6 + ( CH 2 CH 2
) n ( CF2 CF2
) n + HF + XeF4
Determine mass of F2 ( g ) required for preparation of 1.0 kg fluorinated polymer.

Problems

PROBLEM 21 2.5 g of a sample containing Na 2CO 3 ; NaHCO 3 and some non-volatile impurity on
gentle heating loses 12% of its weight. Residue is dissolved in 100 mL water and its 10 mL portion
required 15 mL 0.1 M aqueous solution of BaCl 2 for complete precipitation of carbonates. Determine
mass percentage of Na 2CO 3 in the original sample.
PROBLEM 22 2.0 g of a sample containing NaCl, NaBr and some inert impurity is dissolved in enough
water and treated with excess of AgNO 3 solution. A 3.0 g of precipitate was formed. Precipitate on
shaking with aqueous NaBr gain 0.76 g of weight. Determine mass percentage of NaCl in the original
sample.
PROBLEM 23 Based on the following information, determine value of x and y:
AgNO3

## (CH 3 ) x AlCl y xCH 4 ( g ) + yCl + Al 3+ AgCl( s)

0.643 g

0.222 g

0.996 g

PROBLEM 24 An organic compound containing C, H, O, N and Cl was analyzed and 0.15 g of sample
on combustion produced 0.138 g of CO 2 and 0.0566 g of H 2O. All the nitrogen in different 2.0 g sample
of compound was converted into NH 3 which was found to weigh 0.238 g. Finally the chlorine in a 0.125
g sample of compound was converted to Cl and by reacting with AgNO 3 , 0.251 g AgCl was obtained.
Deduce the empirical formula of the starting organic compound.
PROBLEM 25 A 5.0 g sample of felspar containing Na 2O, K 2O and some inert impurity is dissolved in
dilute HCl solution and NaCl and KCl formed are separated by fractional crystallization. During
crystallization some less soluble impurities also comes out. Mass of NaCl, KCl and impurity
accompanying these salts was found to be 6.47 g. Solid crystal was then re-dissolved and required 300
mL of 0.3 M AgNO 3 for complete precipitation of chlorides. The precipitate thus, obtained was found to
contain 4.23% insoluble impurity. Determine mass percentage of Na 2O and K 2O in the original sample.
PROBLEM 26 Potassium chlorate (KClO 4 ) is made in the following sequence of reactions:
Cl 2 ( g ) + KOH KCl + KClO + H 2O
KClO KCl + KClO 3
KClO 3 KClO 4 + KCl
What mass of Cl 2 is needed to produce 1.0 kg of KClO 4 ?
PROBLEM 27 Titanium oxide (TiO 2 ) is heated in stream of hydrogen to give water and a new oxide
Ti x O y . If 1.598 g TiO 2 produces 1.438 g Ti x O y , what is the formula of new oxide.
PROBLEM 28 A solution of copper sulphate that contain 15% CuSO 4 by weight has a density of 1.169
g/mL. 25 mL portion of this solution was reacted with excess of ammonia solution to form a dark blue
solution. When cooled, filtered and dried, 6.127 g of dark blue solid was obtained. A 0.195g solid was
analyzed for ammonia and required 30.63 mL of 0.1036 M HCl solution to reach the equivalence point.
In a separate analysis, 0.200 g was heated at 110C to drive off water, producing 0.185 g of anhydrous
material. Deduce formula of the compound crystallized out from blue solution assuming that it contain
only one copper atom per formula unit. Also determine the percentage yield of crystallization process.
PROBLEM 29 0.1152 g of a compound containing carbon, hydrogen, nitrogen and oxygen are burned in
oxygen. The gases produced are treated further to convert nitrogen containing product into N 2 . The
resulting mixture of CO 2 , H 2O and N 2 is passed through a CaCl 2 drying tube, which gains 0.09912 g.
The gas stream was then bubbled through water where the CO 2 forms H 2CO 3 . Titration of this solution
required 28.8 ml 0.3283 M NaOH solution to reach the phenolphthalein end point. The excess O 2 was

Problems in Chemistry

removed by reaction with copper metal and the N 2 was collected in a 225 mL measuring bulb where it
exerted a pressure of 65.12 mm of Hg at 25C. In a separate analysis, the molar mass of this compound
was found to be 146 g mol 1 . Deduce molecular formula of the starting compound.

PROBLEM 30 Pb(NO 3 ) 2 and KI reacts in aqueous solution to form an yellow precipitate of PbI 2 . In
one series of experiments, the masses of two reactants varied, but the total mass of the two was held
constant at 5.0 g. What maximum mass of PbI 2 can be produced in the above experiment ?
PROBLEM 31 An element X react with hydrogen leading to formation of a class of compounds that is
analogous to hydrocarbons. 5 g of X forms 5.628 g of a mixture of two compounds of X, XH 4 and X 2 H 6
in the molar ratio of 2 : 1. Determine molar mass of X.
PROBLEM 32 The mineral Argyrodite is a stoichiometric compound that contain silver, sulphur ( 2)
and an unknown element Y ( + 4). The mass-ratio of silver and Y in the compound is,
m( Ag) : m(Y ) = 11.88
Y forms a reddish brown lower sulphide on heating the mineral in stream of H 2 ( g ), in which Y is in
+ 2 state. The residue are Ag 2S and H 2S. To convert 10 g Argyrodite completely, 0.295 L of H 2 ( g )
measured at 400K and 1.0 atmosphere is required. Determine molar mass of Y and empirical formula of
mineral.
PROBLEM 33 Uranium is isolated from its ore by dissolving it as UO 2 (NO 3 ) 2 and separating it as
solid UO 2 (C 2O 4 ) xH 2O. A 1.0 g sample of ore on treatment with nitric acid yielded 1.48 g UO 2 (NO 3 ) 2
which on further treatment with 0.4 g Na 2C 2O 4 yielded 1.23 g UO 2 (C 2O 4 ) xH 2O. Determine weight
percentage of uranium in the original sample and x.
PROBLEM 34 When iodine was added to liquid chlorine in cold condition, orange crystal of a
compound separate out. The amount of chlorine in a sample of crystal was determined by precipitating
AgCl. A 0.467 g sample of crystal gave 0.861 g of AgCl. Deduce empirical formula of the crystal.
PROBLEM 35 Urea is manufactured on large scale by passing CO 2 (g ) through ammonia solution
followed by crystallization. CO 2 for the above reaction is prepared by combustion of hydrocarbons. If
combustion of 236 kg of a saturated hydrocarbon produces as much CO 2 as required for production of
1000 kg of urea, deduce molecular formula of hydrocarbon.
PROBLEM 36 Sodium bicarbonate can be purified by dissolving it in hot water (at 60C), filtering to
remove insoluble impurities, cooling to 0C to precipitate solid NaHCO 3 and the filtering to remove the
solid leaving soluble impurities in solution. Some NaHCO 3 that remain in solution is not recovered. The
solubility of NaHCO 3 in water at 60C is 164 g/L. Its solubility in cold water at 0C is 69 g/L. If a 250 g
impure sample of NaHCO 3 was purified by this method by dissolving first in 250 mL water at 60C and
then crystallizing NaHCO 3 from 100 mL water at 0C, 150 g NaHCO 3 was recovered. Determine
percentage purity of original sample.
PROBLEM 37 A 100 g solution was prepared by dissolving 46 g CuSO 4xH 2O in 54 g of water and
mole fraction of CuSO 4 in solution was found to be 0.05. Determine x.
PROBLEM 38 An ore of iron contain FeS and non-volatile impurity. Roasting of this ore converts all
FeS into Fe 2 O3 and a 4% loss in weight was observed. Determine mass percentage of FeS in ore.
PROBLEM 39 Optical measurement is a very efficient method of determining molar mass of unknown
material. In one experiment, 3.0 g of an unknown polymeric material was dissolved in 100 mL of CCl 4
and transmittance of this solution was found to be 72%. Transmittance of a 0.001 M standard solution in

Problems

the same solvent, under identical experimental condition was 60%. Determine molar mass of unknown
polymer.

PROBLEM 40
shown below,

300
100
3

## If density of this polymer is 1.2 g/cm , determine molar mass.

PROBLEM 41 A mother cell disintegrate into sixty identical cells and each daughter cell further
disintegrate into 24 smaller cells. The smallest cells are uniform cylindrical in shape with diameter of
120 and each cell is 6000 long. Determine molar mass of the mother cell if density of the smallest
cell is 1.12 g/cm 3 .
PROBLEM 42 A sample of rock taken for analysis weigh 1.0 g on air dried basis. After drying for one
hour at 110C, the sample weigh 0.9437 g. The calcium is precipitated as oxalate but weighed as CaSO 4 ;
that weigh 0.5g. The magnesium is precipitated as MgNH 4 PO4 which finally ignited to 0.5 g Mg 2 P2O 7 .
Find the percentage of CaO and MgO on oven dried basis and percentage of them and H 2O on air dried
basis.
PROBLEM 43 A sample is a mixture of Mohrs salt and (NH 4 ) 2 SO 4 . A 0.5 g sample on treatment with
excess of BaCl 2 solution gave 0.75 g BaSO 4 . Determine percentage composition of the salt mixture.
What weight of Fe 2O 3 would be obtained if 0.2 g of the sample were ignited in air?
PROBLEM 44 A chloride mixture is prepared by grinding together pure BaCl 22H 2O, KCl and NaCl.
What is the smallest and largest volume of 0.15 M AgNO 3 solution that may be used for complete
precipitation of chloride from a 0.3g sample of the mixture which may contain any one or all of the
constituents?

ACID-BASE TITRATION
PROBLEM 45 A 1.5 g sample containing oxalic acid and some inert impurity was dissolved in enough
water and volume made up to 250 mL. A 20 mL portion of this solution was then mixed with 30 mL of an
alkali solution. The resulting solution was then treated with stoichiometric amount of CaCl 2 just needed
for precipitation of oxalate as CaC 2O 4 . Solution was filtered off and filtrate was finally titrated against
0.1 M HCl solution. 8.0 mL of acid was required to reach the equivalence point. At last, the above neutral
solution was treated with excess of AgNO 3 solution and AgCl obtained was washed, dried and weighed
to be 0.4305 g. Determine mass percentage of oxalic acid in the original sample.
PROBLEM 46 A 1.5 g sample containing P2O 3 and some inert impurity was dissolved in enough water
and boiled gently where P2O 3 disproportionated quantitatively into PH 3 and H 3 PO 4 . The solution was

Problems in Chemistry

further boiled for some time to let-off all PH 3 ( g ) and finally cooled to room temperature and diluted to
100 mL. A 10 mL portion of this solution was then mixed with 20 mL 0.3 M NaOH solution. Excess
alkali required 11.0 mL 0.05 M H 2SO 4 solution for back titration. Determine mass percentage of P2O 3 in
the original sample.

PROBLEM 47 2.5 g of a mixture containing CaCO 3 , Ca(HCO 3 ) 2 and NaCl was dissolved in 100 mL
water and its 10 mL portion required 10 mL 0.05 M H 2SO 4 solution to reach the phenolphthalein end
point. An another 10 mL portion of the same stock solution required 32.35 mL of the same acid solution
to reach the methyl orange end point. Determine mass percentage of CaCO 3 and Ca(HCO 3 ) 2 in the
original mixture.
PROBLEM 48 A solution contain both Na 2CO 3 and NaHCO 3 . 10 mL portion of this solution is mixed
with few drops of phenolphthalein indicator and titrated against 0.08 M H 2SO 4 solution. 7.0 mL of acid
was required to reach the end point A 5.0 mL portion of this solution was then taken for further analysis
and a few drops of methyl orange was added to it and finally titrated against same acid solution. 3.53 mL
of acid was required to reach the end point. Determine mass of Na 2CO 3 and NaHCO 3 per litre of
solution. Ignore volume change due to addition of indicator.
PROBLEM 49 A mixture was known to contain both KNO 3 and K 2SO 3 . To 0.486 g of the mixture,
dissolved in enough water to give 50 mL solution, was added 50 mL of 0.15 M HCl solution. The
reaction mixture was heated to expel all SO 2 and then 25 mL of the reaction mixture was titrated with 0.1
M KOH. The titration required 13.11 mL of the base. Calculate mass percentage of K 2SO 3 in the
mixture.
PROBLEM 50 An amino acid isolated from a piece of animal tissue was believed to be glycine. A 0.05 g
sample was treated in such a way that all nitrogen in it was converted into ammonia. This ammonia was
added to 50 mL of 0.05 M HCl solution. The excess acid remaining in the solution required 30.57 mL
0.06 M NaOH solution for complete neutralization. What was the percentage by mass of nitrogen? How
does this mass compare with percentage mass of nitrogen calculated from glycine (H 2 NCH 2COOH)?
PROBLEM 51 In a reaction, calcium orthophosphate on heating with magnesium produced calcium
phosphide, magnesium metaphosphate, calcium oxide and oxygen gas. Phosphide on hydrolysis
produces PH 3 gas. The PH 3 gas is burnt completely to P2O 5 using air, which contains 21%, by volume
of oxygen. Calculate the volume of air at STP required for combustion, if 2.4 g Mg was initially reacted
with calcium orthophosphate. All volumes are measured at STP.
PROBLEM 52 9.3 g of a mixture containing Li 2CO 3 , NaHCO 3 , Na 2CO 3 on strong heating produced
7.37 g of solid residue. The residue is dissolved in 200 mL water.
A 10 mL portion of this solution is mixed with 15 mL of a normal HCl solution. The excess acid
required 12 mL 0.5 N NaOH solution to reach the equivalence point. Determine the mass percentage of
NaHCO 3 and Na 2CO 3 in the original mixture. Li = 7, Na = 23.
PROBLEM 53 4.0 g of a monobasic, saturated carboxylic acid is dissolved in 100 mL water and its 10
mL portion required 8.0 mL 0.27 M NaOH to reach the equivalence point. In an another experiment, 5.0
g of the same acid is burnt completely and CO 2 produced is absorbed completely in 500 mL of a 2.0 N
NaOH solution. A 10 mL portion of the resulting solution is treated with excess of BaCl 2 to precipitate
all carbonate and finally titrated with 0.5 N H 2SO 4 solution. Determine the volume of the acid solution
that would be required to make this solution neutral.
PROBLEM 54 5.0 g of a mixture containing NaHCO 3 , NaCl and Na 2CO 3 is dissolved in 500 mL water
and its 10 mL portion required 12.4 mL 0.1 M HCl solution to reach the equivalence point. In an another

Problems

experiment, 10 mL portion of the same stock solution is mixed with 10 mL 0.15 M NaOH solution.
Excess NaOH required 12.6 mL 0.1 M HCl solution for back titration. Determine the mass percentage of
each component in the original mixture.

PROBLEM 55 6.4 g of a pure monobasic organic acid is burnt completely in excess of oxygen and CO 2
evolved is absorbed completely in one litre of an aqueous solution of NaOH. A 10 mL portion of this
solution required 14.5 mL of a normal HCl solution to reach the phenolphthalein end point. An another
10 mL portion of the same solution required 18 mL of the same HCl solution to reach the methyl orange
end point. If the organic acid contains 25% oxygen by weight, deduce the empirical formula of this acid
and strength of original NaOH solution.
PROBLEM 56 A complex of cobalt with ammonia is analyzed for determining its formula, by titrating it
against a standardized acid as follows:
Co(NH 3 ) x Cl 3 ( aq ) + HCl NH +4 ( aq ) + Co 3+ ( aq ) + Cl ( aq )
A 1.58 g complex required 23.63 mL 1.5 M HCl to reach the equivalence point. Determine formula.
If the reaction mixture at equivalence point is treated with excess of AgNO 3 solution, what mass of AgCl
will precipitate out?

PROBLEM 57 One litre solution of alkali is prepared by dissolving impure solid of alkali which contain
5% Na 2CO 3 and 8% CaCO 3 and 10% NaCl. A 10 mL portion of this solution required 9.8 mL of a 0.5 M
H 2SO 4 solution for neutralization. Calculate weight of alkali dissolved initially.
PROBLEM 58 40 g of a sample of caustic soda containing NaOH, Na 2CO 3 and inert impurity is
dissolved in water to prepare 1.0 litre solution. A 25 mL portion of this solution required 23.15 mL 1.022
N HCl for complete neutralization. To 25 mL another solution, excess of BaCl 2 is added, and resulting
solution required 22.55 mL HCl of same strength to reach the end point. Calculate mass percentage of
NaOH and Na 2CO 3 in the original sample.
PROBLEM 59 1.5 g of a sample containing Na 2CO 3 and NaHCO 3 is dissolved in 100 mL of water. A
25 mL portion of this solution required 22.45 mL 0.202 N HCl using methyl orange as indicator. In a
separate analysis, 25 mL portion of the same stock solution is mixed with 30 mL 0.204 N NaOH and then
excess of BaCl 2 is added resulting in precipitation of all carbonate as BaCO 3 . Filtrate required 9.98 mL
HCl of same strength. Calculate mass percentage of Na 2CO 3 and NaHCO 3 in the mixture.
PROBLEM 60 One gram sample of a saturated hydrocarbon is burned completely and liberated CO 2
was absorbed in a 1.0 L 0.2 N NaOH solution. To the resulting solution, excess of BaCl 2 crystals was
added and the solution was filtered off to free from BaCO 3 . A 10 mL portion of the extract required 12
mL 0.025 M H 2SO 4 solution for neutralization. Determine molecular formula of the hydrocarbon.
PROBLEM 61 2.0 g of a saturated, monobasic carboxylic acid was burned and liberated CO 2 was passed
through a concentrated solution of NaOH. The resulting solution was separated into two equal half and
analyzed. One half required 71.72 mL 1.0 N HCl to reach the end point in presence of phenolphthalein
indicator. The other half required 123.44 mL 1.0 N HCl to reach the end point in presence of methyl
orange indicator. Deduce formula of acid and determine mass of NaOH present initially.
PROBLEM 62 2.5 g of a mixture containing NaHCO 3 , Na 2CO 3 and NaCl is dissolved in 100 mL water
and its 50 mL portion required 13.33 mL 1.0 N HCl solution to reach the equivalence point. On the other
hand its other 50 mL portion required 19 mL 0.25 M NaOH solution to reach the equivalence point.
Determine mass percentage of each component.

10

Problems in Chemistry

PROBLEM 63 2.0 g of a crystal of CaCO 3 is dissolved in 50 mL water and then mixed with 50 mL of a
HCl solution. The resulting solution is boiled to remove all CO 2 and its 10 mL portion required 8.0 mL of
a NaOH solution to make the solution neutral. Also 20 mL of original HCl solution is equivalent to 96
mL of NaOH solution. Determine molarity of both NaOH and HCl solution.
PROBLEM 64 2.725 g of a mixture of K 2C 2O 4 , KHC 2O 4 and H 2C 2O 4 2H 2O is dissolved in 100 mL
H 2O and its 10 mL portion is titrated with 0.1 N HCl solution.
20 mL acid was required to reach the equivalence point. In another experiment, 10 mL portion of the
same stock solution is titrated with 0.1 N KOH solution. 20 mL of base was required to reach the
equivalence point. Determine mass percentage of each component in the mixture.
PROBLEM 65 A 1.0 g sample containing NH 4 NO 3 , (NH 4 ) 3 PO 4 and some inert impurity was
dissolved in 100 mL water its 10 mL portion required 15 mL 0.1 M NaOH solution to reach the
equivalence point. In a separate experiment, 10 mL of the same stock solution was treated with excess of
BaCl 2 solution and 0.077 g of barium phosphate precipitate was obtained. Determine mass percentage of
ammonium nitrate in the original sample.
PROBLEM 66 10.38 mg of a diprotic acid (containing (C, H and O) is burned completely and all CO 2
was absorbed in 100 mL of alkali solution. The resulting solution is separated into two-half and one-half
required 55 mL 0.005 M H 2SO 4 solution to reach the phenolphthalein end point. Other half was titrated
in presence of methyl orange indicator and 80 mL H 2SO 4 solution of same strength was required to
reach the end point. In a separate analysis, 0.168 g of the same acid required 16.18 mL 0.125 M NaOH
solution to reach the end point. Deduce formula of the acid and determine molarity of alkali solution used
initially.
PROBLEM 67 A 3.0 g sample containing Na 2CO 3 , NaHCO 3 , NaCl and some inert impurity was
dissolved in 100 mL of water and its 10 mL portion was titrated against 0.1 M HCl solution using
phenolphthalein indicator. 11.32 mL of acid solution was required to reach the end point. The resulting
solution was then mixed with excess of AgNO 3 solution resulting in formation of 0.306 g of AgCl
precipitate. The solution was filtered-off and filtrate was again titrated, but now against 0.05 M NaOH
solution. 42.64 mL of alkali was required to reach the end point. Determine mass percentage of Na 2CO 3 ,
NaHCO 3 and NaCl in the original sample.
PROBLEM 68 In neutralization titration of Na 3 PO 4 , if phenolphthalein is used as indicator, end point is
indicated only when Na 3 PO 4 is converted into Na 2 HPO 4 while, if methyl orange is used as indicator,
end point appear only when Na 3 PO 4 is converted into H 3 PO 4 . In an experiment a 4.0 g mixture
containing Na 3 PO 4 , Na 2 HPO 4 and NaH 2 PO 4 is dissolved in 50 mL water and its 10 mL portion
required 24.4 mL 0.1 M HCl solution to reach the end point using phenolphthalein indicator. In a
separate analysis, 10 mL portion of the same stock solution required 23.572 mL 0.5 M HCl solution to
reach the end point using methyl orange as indicator. Determine mass percentage of all components in
the mixture.
PROBLEM 69 A mixture containing LiHCO 3 , NaCl and Na 2CO 3 on gentle heating loses 26.5% of its
weight. 5.0 g of this mixture was heated gently and residue was dissolved in 100 mL water. A 10 mL
portion of this solution was then treated with 20 mL 0.2 M H 2SO 4 solution. A 10 mL portion of the
resulting solution required 3.86 mL 0.1 M NaOH solution to reach the end point. Determine mass
percentage of each component in the mixture.
PROBLEM 70 A mixture containing LiHCO 3 , NaHCO 3 and CaCO 3 on gentle heating loses 48.4% of
its weight. In an experiment, 5.0 g of this mixture was dissolved in 100 mL water and its 10 mL portion

11

Problems

was treated with 10 mL 0.5 M NaOH solution. The resulting solution was then treated with excess of
BaCl 2 solution resulting in precipitation of all carbonates as BaCO 3 . Precipitate was separated out by
filtration and filtrate required 15.3 mL 0.1 N HCl solution to reach the end point. Determine mass
percentage of all components present in the mixture.

PROBLEM 71 5.0 g of a mixture containing NaCl, NaHCO 3 , Na 2CO 3 and CaCO 3 on gentle heating
reduces to 4.25 g of solid residue. In a separate experiment, 1.0 g of the same mixture required 10 mL 0.2
M NaOH to reach the end point. In a 3rd experiment, 1.0 g of the same mixture was dissolved in 100 mL
water and required 10 mL 1.053 M HCl solution to reach the end point. Determine mass percentage of
each component in the mixture.
PROBLEM 72 2.0 g of a sample of CaCO 3 , NaHCO 3 and some volatile, inert impurity, was heated
strongly where CaCO 3 and NaHCO 3 , were decomposed into CaO and Na 2CO 3 respectively and all CO 2
gas produced in decomposition was absorbed in a 50 mL NaOH solution. NaOH was little less than the
stoichiometric requirement therefore, CO 2 during reaction with NaOH, produced Na 2CO 3 and some
NaHCO 3 . The resulting solution was titrated first in presence of phenolphthalein indicator and 5.0 mL
1.0 M HCl was required to reach the phenolphthalein end point. Methyl orange was then added and
titration continued with HCl of same strength where 15 mL HCl was required to reach the final end point.
On the other hand, the residue obtained after heating of the original sample was dissolved in water
and treated with excess of BaCl 2 , giving 0.985 g of BaCO 3 precipitate. Determine mass percentage of
CaCO 3 and NaHCO 3 in the original sample.
PROBLEM 73 A one gram sample containing NaOH as the only basic substance and some inert
impurity was left exposed to atmosphere for a very long time so that part of NaOH got converted into
Na 2CO 3 by absorbing CO 2 from atmosphere. The resulting sample was dissolved in water and volume
made upto 100 mL. A 100 mL portion of this solution required 16 mL 0.25 M HCl solution to reach the
equivalence point when methyl orange was used as indicator. In a separate analysis, 20 mL portion of the
same solution was taken alongwith phenolphthalein indicator and mixed with 50 mL of 0.1 M HCl
solution. An additional 9.00 mL 0.1 M Ba(OH) 2 solution was required to just restore the pink colour of
solution. Determine mass percentage of NaOH in the original sample and mass percentage of Na 2CO 3 in
the sample after exposure to atmosphere.
PROBLEM 74 The monochloroacetic acid (ClCH 2COOH) preservative in a 100 mL of carbonated
beverage was extracted by shaking with dimethyl ether and then returned to aqueous solution as
ClCH 2COO by extraction with 1.0 M NaOH. This solution was acidified and treated with 50 mL
0.0452 M AgNO 3 solution where the following reaction occurred:
ClCH 2COOH + AgNO 3 + H 2O HOCH 2COOH + H + + NO 3 + AgCl( s)
After filtering the AgCl, titration of filtrate required 10.43 mL of an NH 4SCN solution. Titration of a
blank taken through the entire procedure used 22.98 mL of same NH 4SCN solution. Calculate weight in
mg, of ClCH 2COOH in the beverage sample.

PROBLEM 75 2.0 g of a sample containing sodium oxalate, oxalic acid dihydrate and some inert
impurity was dissolved in 100 mL water and its 20 mL portion required 23.34 mL 0.04 M acidified
permanganate solution to reach the equivalence point. In a separate analysis, 20 mL portion of the same
stock solution required 26.67 mL 0.1 N NaOH solution to reach the end point. Determine mass
percentage of Na 2C 2O 4 and H 2C 2O 42H 2O in the original sample.
PROBLEM 76 A 1.5 g sample containing (NH 4 ) 2 SO 4 , NH 4 NO 3 and some inert impurity was
dissolved in water and volume made upto 100 mL. A 20 mL portion of this solution was mixed with 50

12

Problems in Chemistry

mL 0.1 M NaOH solution. A 30 mL aliquot of this resulting solution required 9.00 mL 1/28 M H 2SO 4
solution for complete neutralization. In a separate analysis, 32 mL of the original stock solution on
treatment with excess of BaCl 2 solution produced 0.466 g BaSO 4 precipitate. Determine mass
percentage of NH 4 NO 3 and (NH 4 ) 2 SO 4 in the original sample.

PROBLEM 77 A 1.0 g impure sample containing [Zn(NH 4 ) 4 ]Cl 2 and some inert impurity was treated
with 15 mL of 1 M NaOH solution where all complex is converted into Na 2 [Zn(OH) 4 ] . The excess base
1
required 10 mL M HCl solution for back titration.
6
(a) Determine percentage purity.
(b) If the last solution obtained after neutralization was treated with excess of AgNO 3 , what weight
of AgCl would have been produced?
PROBLEM 78 1.2 g of a salt with their empirical formula K x H y (C 2O 4 ) z was dissolved in 50 mL of
water and its 10 mL portion required 11.00 mL of a 0.1 M HCl solution to reach the equivalence point. In
a separate analysis, 15 mL of the stock solution required 20 mL 0.2475 M KOH to reach the equivalence
point. Determine empirical formula of the salt.
PROBLEM 79 Impure phosphoric acid for use in the manufacture of fertilizer is produced by the
reaction of sulphuric acid on phosphate rock of which a principal component is Ca 3 (PO 4 ) 2 and rest are
silica and other inert impurity. In an analysis, 2.0 g of a sample of rock salt was dissolved in 100 mL
H 2SO 4 solution. Excess sulphuric acid left in 20 mL of this solution required 40 mL 0.02 M NaOH for
back titration. In a separate analysis 20 mL of the above solution required 50 mL 0.04 M NaOH for
complete neutralization. Determine mass percentage of Ca 3 (PO 4 ) 2 in rock-sample.
PROBLEM 80 A 10 g sample of ammonium perchlorate containing some inert impurity was mixed
with 3 g Al powder where all perchlorate reacted to produce Al 2O 3 , N 2 , HCl and H 2O. All HCl was
absorbed in 100 mL 1 M NaOH solution. Determine percentage purity of perchlorate sample and volume
of 0.5 M HCl required to neutralize the above solution.
PROBLEM 81 Potassium superoxide (KO 2 ) is utilized in closed system breathing apparatus to remove
CO 2 and water from exhaled air. The removal of H 2O generate oxygen gas and KOH and this KOH in the
subsequent step remove CO 2 as KHCO 3 . 5.0 kg of an impure sample of KO 2 is just sufficient to remove
all CO 2 and H 2O from a closed room of dimension 10 m 5 m 3m. Determine mass of this KO 2
required to neutralize a 100 mL 0.1 M H 2SO 4 solution in a separate analysis. Assume room conditions to
be at 1.0 atmosphere and 300 K and mole fraction of CO 2 in that room is 0.01.
PROBLEM 82 3.25 g of a saturated, tribasic carboxylic acid required 68.4 mL of a 0.750 M NaOH
solution to reach the equivalence point. Determine molecular formula of acid.

REDOX TITRATION
PROBLEM 83

## A sample of chrome-vanadium steel weighing 2.0 g was dissolved in a mixture of

sulphuric acid and just sufficient oxidant was added to raise the oxidation state of iron to Fe 3+ , the

chromium to Cr 2O 2
7 , vanadium to VO 3 and Mn to MnO 4 . The solution was then treated with HCl and

## resulting solution still containing Fe 3+ , Cr 2O 2

7 and VO 3 then treated with 25 mL of 0.101 M FeSO 4 .

Problems

13

## This resulted in reduction of dichromate and VO 3 to Cr 3+ and VO 2+ in the solution respectively. Fe 2+

and VO 2+ in the solution was then titrated with 0.02236 M KMnO 4 and required 12.6 mL to reach the
equivalence point. A small amount of Fe 2+ was then added to again reduce the VO 3 produced by
KMnO 4 back to VO 2+ and this then titrated directly with 0.02236 M KMnO 4 , a process requiring 0.86
mL to reach the equivalence point. Calculate the following quantities:
(a) Moles of Fe 2+ in 25 mL sample of standard FeSO 4 solution.
(b) Moles of Fe 2+ titrated with 12.6 mL of standard KMnO 4 .
(c) Moles of Fe 2+ consumed by Cr 2O 2
7 .
(d) Percentage of V and Cr in the steel
[Atomic weight of V = 51, Cr = 52]

PROBLEM 84 A sample of crude uranium oxide is known to be contaminated with iron. To determine
the extent of contamination, the crude oxide were dissolved and reduced with Zn to yield a solution
containing U 4+ and Fe 2+ . A 20 mL aliquot of this solution was treated with cupferron which precipitated
all uranium and the resulting precipitate on ignition yielded 423.3 mg of U 3O 8 . A further 20 mL sample
was treated with 0.024 M KMnO 4 solution and consumed 27.23 mL. Calculate mass percentage of
contamination if the iron were present as Fe 2O 3 in a sample of crude oxide containing 100 g of U 3O 8 .
KMnO 4 solution oxidised Fe 2+ to Fe 3+ and U 4+ to UO 2+
2 . Atomic mass of U = 238.
PROBLEM 85 A 5.0 g sample containing Pb 3O 4 , PbO 2 and some inert impurity is dissolved in 250 mL
dil. HNO 3 solution and 2.7 g of Na 2C 2O 4 was added so that all lead converted into Pb 2+ . A 10 mL
portion of this solution required 8.0 mL 0.02 M KMnO 4 for titration of excess of oxalate. In an another
experiment, 25 mL of solution was taken and excess oxalate was removed by extraction, this required 10
mL of a permanganate solution for oxidation of Pb 2+ to Pb 4+ . 10 mL this permanganate solution is
equivalent to 4.48 mL 5 V H 2O 2 solution. Calculate mass percentage of PbO 2 and Pb 3O 4 in the original
sample.
[Atomic mass of Pb = 207]
PROBLEM 86 An unknown cupric salt with formula Cu x (CO 3 ) y (OH) z is analyzed to determine the
exact formula. A 1.7225 g sample of salt was dissolved in 100 mL of pure water. A 50 mL portion of this
solution required 10 mL 1.0 N H 2SO 4 solution to reach the equivalence point if phenolphthalein was
used as indicator. Another 50 mL portion was titrated using methyl orange as indicator and 15 mL acid of
same strength was required. Deduce the formula of the salt.
PROBLEM 87 Both CaCl 2 and NaCl are used to melt ice and snow on roads in winter. A certain
company was marketing a mixture of these two compounds for this purpose. A chemist, wishing to
analyze the mixture, dissolved 1 g of it in water and precipitated the calcium by adding sodium oxalate.
The calcium oxalate was then carefully filtered, dissolved in dilute sulphuric acid, and titrated with 0.1
M KMnO 4 solution. The titration required 22 mL of the KMnO 4 solution. Calculate freezing point of an
aqueous solution which is 5% (w/V) of the above mixture. K f of water is 1.86 K kg mol 1 .
PROBLEM 88 A 4.25 g sample containing CaC 2O 4 , Na 2C 2O 4 and some inert impurity is heated gently
so that CaC 2O 4 decomposed as:
CaC 2O 4 CaO + CO( g ) + CO 2 ( g )

14

Problems in Chemistry

All gaseous products were passed through a NaOH solution where following reaction occurred
quantitatively:
2NaOH + CO 2 ( g ) Na 2CO 3
The resulting solution is separated into two equal part (by volume) and one part required 30 mL
0.5 M HCl to reach the phenolphthalein end point while the other half solution required 50 mL 0.5 M
HCl solution to reach the methyl orange end point. In a separate experiment same mass of the same
sample is dissolved into 100 mL dilute HCl solution and its 10 mL portion required 10 mL 0.1 M
K 2Cr 2O 7 solution. Determine the mass percentage of Na 2C 2O 4 in the original sample.

## PROBLEM 89 In acidic solution, 45 mL KMnO 4 solution is required to react with 50 mL 0.25 N

Na 2C 2O 4 solution. How many mL of this same KMnO 4 solution would be required to oxidise 25 mL 0.1
N K 2C 2O 4 solution in alkaline medium where KMnO 4 is reduced to MnO 2 .
PROBLEM 90 A sample weighing 0.3 g containing K 3 [Fe(C 2O 4 ) 3 ] 3H 2O,FeCl 3 6H 2O and inert
impurity is dissolved in dilute sulphuric acid and volume made up to 100 mL. A 20 mL portion of this
solution required 3.75 mL of 0.005 M acidified KMnO 4 solution to reach the equivalence point. In an
another experiment, 50 mL sample of the same stock solution is treated with Zn-amalgum and the
resulting solution required 17.5 mL of permanganate solution of same strength. Determine mass
percentage of FeCl 3 6H 2O in the original sample.
PROBLEM 91 A 6.1 g sample containing oxalic acid dihydrate, sodium oxalate and NaHC 2O 4 and is
dissolved in 100 mL of water and its 10.0 mL portion required 16 mL 0.25 M HCl to reach the
equivalence point. In another experiment 10.0 mL portion of the same stock solution required 24 mL
0.25 M NaOH to reach the equivalence point. Determine the mass percentage of all components in the
original mixture.
PROBLEM 92 A 0.127 g of an unsaturated oil was treated with 25 mL of 0.1 M ICl solution. The
unreacted ICl was then treated with excess of KI. Liberated iodine required 40 mL 0.1 M hypo solution.
Determine mass of I 2 that would have been required with 100.0 g oil if I 2 were used in place of ICl.
PROBLEM 93 Alkali metal nitrate on heating decomposes to metal nitrite and oxygen whereas alkaline
earth metal on heating decomposes into metal oxide, NO 2 and oxygen. In an experiment 15 g mixture of
NaNO 3 and Mg(NO 3 ) 2 was heated until no more gas were evolved. The water soluble part of residue
was used for analysis and dissolved in 1.0 litre water. 10 mL portion of this solution was reacted with 20
mL 0.02 M acidified KMnO 4 solution. The excess reagent required 10.00 mL 0.05 M oxalic acid
solution. Determine mass percentage of each nitrate in the mixture. Also determine the molar ratio of
oxygen to NO 2 in the gaseous products given off.
PROBLEM 94 The mass percentage of MnO 2 in a sample of mineral is determined by reacting with
As 2O 3 in acid solution. A 0.225 g sample of mineral is ground and boiled with 75 mL 0.0125 M As 2O 3
solution. After the reaction is complete, the solution is cooled and titrated with 2.28 10 3 M acidified
KMnO 4 solution. 16.34 mL of the oxidizing agent solution was required to reach the end point.
Determine mass percentage of MnO 2 in the sample.
PROBLEM 95 A driver is arrested and asked to pass breath analyzer test. A sample consisting 56.5
mL of exhaled air is then bubbled into a spectrometer cell containing 3 mL 0.025% (w/V) K 2Cr 2O 7
solution. The transmittance of the solution was 41.5% initially and 43.4% after bubbling the sample

Problems

15

through the reaction cell. It is known that the alcohol content in blood stream is 2300 times higher than in
exhaled air and that the legal limit is 80 mg of alcohol per 100 mL of blood. Determine the concentration
of alcohol in the blood and state whether or not the driver should be charged with drunk driving.

PROBLEM 96 A sample of 0.3657 g powder containing only Ba(NO 3 ) 2 and Ca(NO 3 ) 2 are dissolved in
50 mL water. Ammonia is added to the solution to raise the pH than an excess of Na 2C 2O 4 is added to
precipitate the metals. The precipitate is then filtered, washed with 1.0 L of water and transferred to a
beaker containing 50 mL H 2O. The solution is acidified to solublise the precipitate and finally titrated
with 0.05 M KMnO 4 solution. A total of 13.94 mL of oxidizing agent solution was required to reach the
end point. Find the composition of the initial mixture. K sp. of BaC 2O 4 = 1.5 10 8 and of
CaC 2O 4 = 2.34 10 9 .

PROBLEM 97 1.0 g sample containing KO 2 and some inert impurity is dissolved in excess of aqueous
HI solution and finally diluted to 100 mL. The solution is filtered off and 20 mL of filtrate required 15
mL 0.4 M Na 2S 2O 3 solution to reduce the liberated iodine. Determine mass % of KO 2 in the original
sample.
PROBLEM 98 Cuprous ion is known to disproportionate quantitatively in acid medium. A 3.0 g sample
of Cu 2O is dissolved in dilute H 2SO 4 solution. The solution is filtered off and 8.3 g pure KI crystal is
added to filtrate. This caused precipitation of CuI with evolution of I 2 . The solution is filtered off and
filtrate is boiled till all I 2 is expelled off. Now, excess of an oxidizing agent is added to filtrate and
liberated iodine required 10 mL 1.0 N Na 2S 2O 3 solution. Calculate mass percentage of Cu 2O in the
original sample.
PROBLEM 99 To a 10 mL 1.0 M aqueous solution of Br 2 , excess of NaOH is added so that all Br 2
disproportionated to Br and BrO 3 . The resulting solution is freed from bromide ion by extraction and
excess of OH neutralized by acidifying the solution. The resulting solution is just sufficient to react
with 1.5 g of an impure CaC 2O 4 sample. Calculate percentage purity of oxalate sample.

PROBLEM 100 One gram of an impure sample of NaCl was dissolved in water and treated with excess
of AgNO 3 solution. The precipitate AgCl thus, formed undergo decomposition into Ag and Cl 2 ( g ) and
latter disproportionate into chlorate (V) and chloride ions and chloride is re-precipitated due to presence
of excess of AgNO 3 . If the original precipitate was 60% decomposed and final precipitate weigh 1.5
gram, determine mass percentage of NaCl in original sample.
PROBLEM 101 0.4 g of a sample containing CuCO 3 and some inert impurity was dissolved in diute
sulphuric acid and volume made up to 50 mL. To this solution was added 50 mL 0.04 M KI solution
where copper precipitate as CuI and iodide ion is oxidized into I 3 . A 10 mL portion of this solution is
taken for analysis, filtered, made free from I 3 and treated with excess of acidic permanganate solution.
Liberated iodine required 20 mL 2.5 m M sodium thiosulphate solution to reach the end point. Determine
mass percentage of CuCO 3 in the original sample.

PROBLEM 102 One gram of an unknown sample of NaCN is dissolved in 50 mL 0.33 M alkaline
solution of KMnO 4 and refluxed so that all cyanide is converted into cyanate (OCN ). The reaction
mixture was cooled and its 5.0 mL portion was acidified by adding excess of sulphuric acid solution and

16

Problems in Chemistry

finally titrated with 19.0 mL 0.1 M FeSO 4 solution. Determine mass percentage of NaCN in the original
sample.

PROBLEM 103 5.0 mL of a pure liquid toluene is dissolved in 100 mL of dilute alkaline KMnO 4
solution and refluxed so that all toluene is oxidized into benzoic acid and a dark brown precipitate of
MnO 2 is formed. Solution is filtered off and filtrate and precipitate were analyzed separately. Precipitate
was re-dissolved into 100 mL 1.0 M acidified solution of Na 2C 2O 4 and excess of oxalate required 50.73
mL 0.1 M acidic dichromate solution for back titration. On the other hand 10.5 mL of filtrate was
acidified by adding excess of sulphuric acid and titrated with 0.1 M acidified solution of Na 2C 2O 4 . A 38
mL of oxalate solution was required to reach the end point. Determine density of liquid toluene and
molarity of original permanganate solution.
PROBLEM 104 A 2.0 g sample containing CaOCl 2 and NaOCl is dissolved in 100 mL water and its 10
mL portion was titrated against 0.15 M acidified solution of Na 2C 2O 4 . 10 mL of oxalate solution was
required to reach the end point. Titrated solution was then treated with excess of aqueous solution of
AgNO 3 where all chloride precipitates as AgCl and weighed to be 0.287 g. Determine mass percentage
of CaOCl 2 and NaOCl in original sample.

GASEOUS STATE
PROBLEM 105 6.0 g of He having average velocity 4 10 2 ms 1 is mixed with 12.0 g of Ne 20 having
the same average velocity. What is the average kinetic energy per mole in the mixture?
PROBLEM 106 The valve of a commercial cylinder of N 2 gas was left slightly open so that small
amount of gas leaked into the laboratory. The leak rate was proportional to the pressure difference
(internal pressure one atm). If the initial leak rate was found to be 1 g s 1 and initial pressure inside the
7.28 m 3 tank was 17180 kPa, what would be the pressure inside the tank after 10 days assuming
temperature of the lab to be 27C.
PROBLEM 107 Calculate pressure exerted by 22.0 g of CO 2 in 0.5 L bulb at 300 K assuming it to be real
gas with a = 363 kPaL2 mol 2 and b = 42.67 cc/ mol.
PROBLEM 108 Molar volume of He at 10.1325 Mpa and 273 K is 0.011075 times its molar volume at
101.325 kPa. Calculate radius of He atom assuming negligible a.
PROBLEM 109 A gas mixture containing 5% by mass of butane and 95% by mass of Ar (40) is to be
prepared by allowing gaseous butane to fill an evacuated 40 L cylinder at 1.0 atm and 27C. Calculate
mass of Ar that gives the desired composition and total pressure of the final mixture.
PROBLEM 110 Cl 2O 7 gas decomposes as:
Cl 2O 7 Cl 2 + O 2
A partially decomposed gaseous mixture is allowed to effuse through a pin-hole and the gas coming

Problems

17

out initially was analyzed. The mole fraction of the O 2 was found to be 0.60, determine the degree of
dissociation.

PROBLEM 111 Proportion of a lighter isotope in a gaseous mixture containing both heavier and lighter
isotopes is increased by successive effusion of the gas mixture. A sample of neon gas has
22
Ne = 90% and 20 Ne = 10% by moles. In how many stages of successive effusion, 25% enrichment of
20
Ne would be achieved?
PROBLEM 112 The density of vapour of a substance at 1.0 atm and 500 K is 0.35 k/ m 3 . The vapour
effuses through a small hole at a rate of 1.33 times faster than oxygen under similar condition.
(a) Determine (i) Molecular weight (ii) Molar volume (iii) Compression factor (Z) of the
vapour (iv) Which forces among the gas molecules are dominating, the attractive or repulsive?
(b) If the vapour behaves ideally at 1000 K, determine the average translational kinetic energy
possessed by a molecule.
PROBLEM 113 Using van der Waals equation of state, calculate the pressure correction factor for two
moles of a gas confined in a four litre flask that exert a pressure of 11 atmosphere at 300 K.
b = 0.05 L mol 1 .
PROBLEM 114 For a van der Waals gas Z (compressibility factor) was found to be 1.5 at 273 K and one
atmosphere and TB of the gas is 107 K. Determine value of a and b.
PROBLEM 115 A flask containing 2.0 moles of He gas at 1.0 atm and 300K is connected to another
flask containing N 2 ( g ) at the same temperature and pressure by a narrow tube of negligible volume.
Volume of the nitrogen flask is three times volume of He-flask. Now the He-flask is placed in a
thermostat at 200 K and N 2 -flask in another thermostat at 400 K. Determine final pressure and final
number of moles in each flask.
PROBLEM 116 In a spherical glass flask A of radius 1.0 m, containing 300 g H 2 (g ), there was a rubber
balloon B containing some N 2 ( g ). Inside B, there was another rubber balloon C containing some oxygen
gas. At 27C, it was found that the balloon B had radius 60 cm and of C was 30 cm. Calculate the total
weight of the gas inside the flask. Now 50 g H 2 ( g ) is further added to A, what would be the volume of B
and C.
PROBLEM 117 A partially decomposed PCl 5 (g ) along with its dissociation product is subjected to
diffusion study and the gases coming out initially collected in an another flask. The rate of effusion of
collected gaseous mixture was found to be 0.45 times rate of effusion of pure oxygen gas. Determine the
degree of dissociation of PCl 5 ( g ) in the original sample.
PROBLEM 118 One mole of a monoatomic gas confined in a 22.5 litre flask at 273 K exert a pressure of
0.98 atm, whereas expected pressure was 1.0 atm has the gas behaved ideally. Determine the van der
Waals constants a and b and Boyles temperature (TB ).
PROBLEM 119 One litre of a gas at 300 atm and 473 K is compressed to a pressure of 600 atm and 273
K. The compressibility factors found to be 1.072 and 1.375 respectively at the initial and final states.
Calculate the final volume.
PROBLEM 120 Calculate the van der Waals constants for ethylene. TC = 282 K,PC = 50 atm.

18

Problems in Chemistry

PROBLEM 121 The second Virial coefficient of an imperfect gas is 2 10 2 (L/ mol) 2 . Calculate the
volume of a gm mole of the gas at 27C and 5 atmosphere pressure.
PROBLEM 122 The van der Waals constant b of a gas is 4.42 centilitre/mol. How near can the centres
of the two molecules approach each other?
PROBLEM 123 For carbon dioxide, critical density is 0.45 g/cc and its TC = 300 K. Determine its van
der Waals constants.
PROBLEM 124 The Virial equation for ethane gas is given by PV = RT + BP . At 0C,
B = 0.1814 L/ mol. Calculate volume of one mole of ethane at 10 atm, and a.
PROBLEM 125 An unknown gas (X) at 2.0 atmosphere and Ar (40) at 1.0 atmosphere were injected
simultaneously from the two ends of a 1.0 metre long glass tube and the first collision between X and Ar
occurred at a distance of 38 cm from Ar-end.Determine the molar mass of X assuming that gases were
injected at same temperature and through the pin-hole of identical geometry.
PROBLEM 126 Using van der Waals equation of state, calculate pressure developed by 100 g of CO 2
contained in a volume of 5.0 litre at 40C. Also compare this value with that calculated using ideal gas
law and determine the percentage deviation from ideality. a = 3.6 atm L2 mol 2 , b = 44 cm 3 mol 1 .
PROBLEM 127 An equation of state for a non-ideal gas can be written as: PVm = A + BP + CP 2 ; where
Vm is the molar volume and P is the gas pressure in atmosphere. B = 2.879 10 2 and C = 14.98 10 5
in litre atmosphere unit. Under the experimental condition, determine the pressure at which PV-P curve
will attain minimum.

PROBLEM 128 A modified form of van der Waals equation of state for 1.0 mole of gas is given as:

P +
(V ) = RT

TV 2
Deduce expression for the first Virial coefficient (B) and Boyles temperature in term of and if
Virial equation of state is:
PV
B C
= 1 + + 2 +
RT
V V

PROBLEM 129 Assuming that dry air contain 79% N 2 and 21% O 2 by volume, calculate the density of
moist air at 25C and 1.0 atmosphere when the relative humidity is 60%. The vapour pressure of water at
25C is 23.76 mm of Hg.
PROBLEM 130 At what temperature, three moles of SO 2 will occupy 10 litre at a pressure of 15.0 atm if
it is a van der Waals gas with a = 6.71 atm L2 mol 2 and b = 56.4 cm 3 mol 1 .
PROBLEM 131 Pressure of He gas confined in a steel chamber drops from 4.0 to 1.0 atmosphere in 4.0
hours due to diffusion through a pin-hole in the steel chamber. If an equimolar mixture of He and
methane gas at 20 atmosphere and the same temperature are confined in the same chamber, what will be
the partial pressure of He and methane after 1.0 hour. Assume rate of diffusion to be linear function of
gas pressure and inverse function of square root of molar masses.
PROBLEM 132 One mole of a van der Waals gas at 0C and 600 atmosphere occupies 0.075 L. If

19

Problems

b = 0.024 L mol 1 , determine compressibility factor (Z) and predict the type of force dominating among
the gas molecule.

PROBLEM 133 A one litre flask containing NH 3 (g ) at 2.0 atmosphere and 300 K is connected to
another 800 mL flask containing HCl(g) at 8.0 atmosphere and 300 K by means of a narrow tube of
negligible volume and gases were allowed to react quantitatively as:
CH4
5.0 atm.

He
2.0 atm.

## NH 3 ( g ) + HCl( g ) NH 4Cl( s); H = 43kJ/ mol

If heat capacity of HCl(g) CV is 20 JK 1 mol 1 , determine final pressure inside the flask assuming
negligible heat capacity of flask and negligible volume of solid NH 4Cl.

PROBLEM 134 A long cylindrical glass tube, equipped with a porous disc at the centre, contain
methane gas at 5.0 atmosphere on one side and He gas at 2.0 atmosphere on the other side of the disc as
shown in the diagram below:
Disc is permeable to both gases and rate of diffusion is directly proportional to the gas pressure and
inversely proportional to square root of molar masses as:
dp
P
where, k is a constant.

=k
dt
M
If k for the diffusion of methane gas is 2.5 10 2 second 1 , determine time after which pressure of
methane chamber will drop to 4.0 atmospheres.

PROBLEM 135 At a given condition of temperature, rate of change of r.m.s. of He gas is twice the rate
of change of absolute temperature. Determine rms of He in the given condition.
PROBLEM 136 1.6 moles of ammonia gas at 300 K is taken in a 2.0 litre flask, sealed and heated to 500
K. At this temperature, ammonia is partially decomposed into N 2 and H 2 and a pressure measurement at
this point gave 48.5 atmosphere. Determine number of moles of each component present at 500 K.
PROBLEM 137 Decomposition of KClO 3 produces oxygen gas and KCl solid. In a typical experiment,
some KClO 3 was decomposed and 36.00 mL oxygen gas was collected over water at 23C. The
laboratory barometer reads 751 mm and vapour pressure of water at 23C is 21.1 mm of Hg. Find the
volume of the dry oxygen at 0C and 1.0 atmosphere.
PROBLEM 138 A narrow tube of negligible volume connects two evacuated bulb of 1.0 litre capacity
each. One bulb is placed in a 200 K thermostat bath and other in a 300 K thermostat bath and then 1.0
mole of an ideal gas is injected into the system. Find the pressure in the two flasks.
PROBLEM 139 Isothermal compressibility ( ) of a gas is defined as:
1 V
=

V P T , n
Determine isothermal compressibility for an ideal gas at 1.0 atmosphere.

PROBLEM 140 What will be the temperature difference needed in a hot air balloon to lift 1.0 kg weight.
Assume that the volume of balloon is 100 m 3 , the temperature of atmosphere is 25C and pressure is 1.0
atmosphere. Average molar mass of air is 29 amu.

20

Problems in Chemistry

PROBLEM 141 Using van der Waals equation of state, find pressure at which the PV vs P curve
acquires minima for 1.0 mole of oxygen gas at 0C. a =1.36 L2 atm mol 2 , and b = 32 cm 3 mol 1 .
PROBLEM 142 The van der Waals constant a is a correction factor to the ideal gas law for
intermolecular force of attractions within the substance. Match the following values of a (
L2 atm mol 1 ): 0.2107, 5.464, 18.00 and 24.06 with gases benzene, toluene, Ne and steam.
PROBLEM 143 The van der Waals constant b is a correction factor to the ideal gas law for the
intrinsic volume of the molecule. Match the following values of b(L mol 1 ): 0.017, 0.0305, 0.1154 and
0.1463, with the gases: toluene, benzene, Ne and steam.

THERMOCHEMISTRY
PROBLEM 144 The specific heat capacity of water is 4.18 J( C) 1 g 1 and that of copper is
0.38 J( C) 1 g 1 . Calculate the heat that must be supplied to a 500 g copper kettel containing 450 g of
water to raise its temperature from 25C to the boiling point of water. What percentage of heat is used to
raise the temperature of the water?
PROBLEM 145 How much heat can be produced from a reaction mixture of 50 g of iron (III) oxide and
25 g of aluminium in the thermite reaction:
Fe 2O 3 ( s) + 2Al( s) Al 2O 3 ( s) + 2Fe( s); H = 851.5 kJ/ mol
PROBLEM 146 Calculate the reaction enthalpy for the hydrogenation of ethyne to ethane, given
standard enthalpy of combustion of ethyne, ethane and hydrogen; 1300, 1560 and 286 kJ/mol
respectively.
PROBLEM 147 Calculate the reaction enthalpy for the synthesis of HCl(g) from the following data:
NH 3 ( g ) + HCl( g ) NH 4Cl( s) H = 176 kJ
N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g ) H = 92.22 kJ
N 2 ( g ) + 4H 2 ( g ) + Cl 2 ( g ) 2NH 4Cl( s) H = 628.86 kJ
PROBLEM 148 An important reaction that occurs in the atmosphere is
NO 2 ( g ) NO( g ) + O( g )
Which is brought about by the sunlight. How mucy energy the sun to cause it must supply? Given,
dissociation energy of oxygen = 498 kJ/ mol and
NO( g ) + O 3 ( g ) NO 3 ( g ) + O 2 ( g ) H = 200 kJ
3O 2 ( g ) 2O 3 ( g )
H = 285.4 kJ
PROBLEM 149 Using reaction a, b and c determine the enthalpy change of this reaction:
3
CH 4 ( g ) + O 2 ( g ) CO( g ) + 2H 2O( g )
2
(a) CH 4 ( g ) + 2O 2 ( g ) CO 2 ( g ) + 2H 2O( g )
H = 802 kJ/ mol

21

Problems

(b) CH 4 ( g ) + CO 2 ( g ) 2CO( g ) + 2H 2 ( g )

## H = + 247 kJ/ mol

PROBLEM 150 The bond energy of H 2 (g ) is 436 kJ/mol and that of N 2 (g ) is 941.3 kJ/mol. Calculate
the average bond energy of an NH bond in ammonia if H f of ammonia is 46 kJ/mol.
PROBLEM 151 The heat of formation of PCl 3 and PH 3 are 306 kJ/mol and 8 kJ/mol respectively, and
the heats of atomization of phosphorus, chlorine and hydrogen are 314, 121 and 216.5 kJ/mol
respectively. Calculate P-Cl and P-H bond energy.
PROBLEM 152 At 25C, the molar heat of formation of SO 2 and H 2O are 296.81 and 285.83 kJ
respectively. Using the information from the following reactions,
2H 2S( g ) + Fe( s) FeS 2 + 2H 2 ( g )
H = 137 kJ/ mol
3
H 2S( g ) + O 2 ( g ) H 2O( l) + SO 2 ( g )
H = 562 kJ/ mol
2
Calculate heat of formation of H 2S( g ) and FeS 2 ( s) at 25C.
PROBLEM 153 The standard molar enthalpy of formation of cyclohexane (l) and benzene (l) at 25C
are 156 and + 49 kJ/ mol respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at
25C is 119 kJ/ mol. Use this data to estimate the magnitude of the resonance energy of benzene.
PROBLEM 154 For the reaction cis-2-butene trans-2-butene and cis-2-butene 1-butene,
H = 950 and +1771cal/ mol respectively. The heat of combustion of 1-butene is 649.8 kcal/mol.
Determine the heat of combustion of trans-2-butene. Also calculate the bond energy of C==C bond in
trans-2-butene. Given B.E of C==O =196, OH =110, O==O = 118, CC = 80 and CH = 98 kcal/mol
respectively. H v (H 2O) = 11 kcal / mol.
PROBLEM 155 Using the data (all values are in kJ/mol at 25C) given below:
(i) Enthalpy of polymerization of ethylene = 72.
(ii) Enthalpy of formation of benzene(l) = 49
(iii) Enthalpy of vaporization of benzene(l) = 30
+ 3H2(g)
(iv) Resonance energy of benzene(l) = 152
(v) Heat of formation of gaseous atoms from the elements in their standard states H = 218, C = 715.
Average bond energy of CH = 415. Calculate the B.E. of CC and C==C. [ A : 331 and 590 kJ/mol]

PROBLEM 156 Calculate energy of aromatization of cyclohexane according to the following reaction,
both cyclohexane and benzene are in liquid state:
Given, bond energies: CC = 348, CH = 415, C==C = 600, HH = 436 kJ/mol respectively,
sublimation energy of C(gr) is 717 kJ/mol, resonance energy of C 6 H 6 ( l) = 152 kJ/ mol, H v of
benzene = 30.8 and of cyclohexane is 33 kJ/mol.
PROBLEM 157 Enthalpy of polymerization of ethylene and acetylene into corresponding polymers are
86 kJ/ mol and 148 kJ/mol respectively. Enthalpy of hydrogenation of ethylene is 132 kJ/mol,
determine C==C bond energy. B.E. of H 2 ( g ) is 436 kJ/mol and of CH = 415 kJ/ mol.

22

Problems in Chemistry

PROBLEM 158 HComb of methane and ethane are 210 kcal/mol and 368 kcal/mol respectively.
Determine HComb of decane.
PROBLEM 159 Determine resonance energy of benzene [C 6 H 6 (l)] from the following information :
H f of C 6 H 6 ( l) = + 49 kJ;
H f of C 2 H 2 ( g ) = + 75 kJ H v of C 6 H 6 ( l) = + 45 kJ
B.E.
C C = 930 kJ/ mol; C==C = 615 kJ/ mol; C C = 348 kJ/ mol
PROBLEM 160 Consider the following thermodynamic data:
Enthalpy of formation of CaC 2 ( s) = 60 kJ/ mol;
Enthalpy of sublimation of Ca( s) = 179 kJ/ mol;
Enthalpy of sublimation of C( s) = 718 kJ/ mol;
First ionization energy of Ca(g) = 590 kJ/ mol;
Second ionization energy of Ca(g) 1143 kJ/mol;
Bond energy of C 2 ( g ) = 614 kJ/ mol;
First electron affinity of C 2 ( g ) = 315 kJ/ mol;
Second electron affinity of C 2 ( g ) = + 410 kJ/ mol.
Draw a clear Born-Haber cycle and determine lattice energy of CaC 2 ( s).
PROBLEM 161 Normal L.P.G. contains 90% propane and 10% methane by weight. If combustion of
L.P.G. produces acetylene, CO(g) and H 2O( l), calculate the heat evolved by combustion of 100 g of
L.P.G.
Given: enthalpy of combustion of methane = 890 kJ/ mol, C 3 H 8 = 2220 kJ/ mol,
C 2 H 2 = 1300 kJ/ mol and CO( g ) = 285 kJ/ mol.
PROBLEM 162 A swimmer breaths 20 times in one minute when swimming and inhale 200 mL of air in
one breath. Inhaled air contain 20% O 2 by volume and exhaled air contain 10% O 2 by volume. If all
oxygen are consumed in combustion of glucose in the body and 25% of energy obtained from
combustion is available for muscular work. Determine the maximum distance this swimmer can swim in
one hour if 100 kJ energy is required for 1.0 km swimming. Standard molar enthalpy of combustion of
glucose is 2880 kJ/ mol and body temperature is 37C.
PROBLEM 163 Standard molar enthalpies of formation of H 2O(l) and H 2O 2 (l) are 285 and 200

kJ/mol respectively and their molar enthalpies of vaporization are 41 and 60 kJ respectively. If enthalpy
of atomization of O 2 ( g ) is 298 kJ/mol, determine bond energy of OO bond.

PROBLEM 164 Determine resonance energy of 1,3-butadiene using the following information:
Enthalpy
of
combustion
:
= 2841 kJ/ mol, C(gr ) = 394 kJ/ mol,
H 2 ( g ) = 285 kJ/ mol
Bond enthalpy : CC = 348 kJ/ mol, C==C = 615 kJ/ mol. Also standard enthalpy of formation of
cyclobutene =130 kJ/ mol,
PROBLEM 165 Standard molar enthalpy of formation of hydrazine liquid (N 2 H 4 ) is 50 kJ/mol,
NH 3 ( g ) = 46 kJ/ mol. Average NH and HH bond energies are 393 and 436 kJ/mol respectively. If
enthalpy of vaporization of N 2 H 4 is 18 kJ/mol, determine NN bond energy in N 2 H 4 .
PROBLEM 166 Using following standard enthalpies:
H f HF( aq ) = 329 kJ/ mol H f H 2O( l) = 285 kJ/ mol,

23

Problems

## H f F ( aq ) = 320 kJ /mol and

H + ( aq ) + OH ( aq ) H 2O( l), H = 56 kJ/ mol.
Determine enthalpy of neutralization of HF against a strong base.

PROBLEM 167 From the following reactions and thermal information at 25C:
3
2Fe( s) + O 2 Fe 2O 3 ( s)
H = 821.4 kJ
2
1
2FeO( s) + O 2 Fe 2O 3 ( s)
H = 284 kJ/ mol
2
Fe( s) + 2H + ( aq.) Fe 2+ ( aq.) + H 2 ( g )
H = 87.8 kJ
1
H ( g ) H + ( aq.)
2 2
1
H 2 ( g ) + O 2 ( g ) H 2O( l)
2
Calculate H for the reaction :

H = 0
H = 285 kJ

FeO( s) + 2H + ( aq ) H 2O( l) + Fe 2+ ( aq )

PROBLEM 168 A 150 cc portion of 0.4 N HCl is neutralized with excess of NH 4OH in a bomb
calorimeter which results in a temperature rise of 2.36C. If the heat capacity of calorimeter content is
1316.7 J/C, calculate heat of neutralization of HCl Vs NH 4OH.
PROBLEM 169 Determine SS bond energy;
Given H f of (C 2 H 5 ) 2 S( g ) = 147 kJ/ mol,
H f of (C 2 H 5 ) 2 S 2 ( g ) = 202 kJ/ mol and H Sublimation of S( s) = 223 kJ/ mol.
PROBLEM 170 Given the following standard molar enthalpies:
of
H f of
CH 3CN( g ) = 88 kJ/ mol,
H f of
C 2 H 6 = 84 kJ/ mol,
H Sublimation
C(gr) = 717 kJ/ mol, bond dissociation energy of N 2 ( g ) and H 2 ( g ) are 946 and 436 kJ/mol respectively,
B.E. (CH) = 410 kJ/mol. Determine CC and C N bond energies.
PROBLEM 171 Determine standard state enthalpy of the following reaction:
CH 3COOH( l) CH 4 ( g ) + CO 2 ( g )
Given H Combustion CH 4 = 860 kJ/ mol. Bond energies in kJ/mol. CH = 410, CC = 348, C==O
= 728, CO = 352, OH = 463, O==O = 498. H Vaporization of acetic acid and water are 52 and 41
kJ/mol respectively.
PROBLEM 172 H f of
enthalpy
of
combustion
of
C 2 H 5OH( l) = 66 kcal/ mol,
CH 3OCH 3 ( g ) = 348 kcal/ mol, H f of water is 68 kcal/mol and H f of CO 2 ( g ) = 94 kcal/ mol.
Determine enthalpy of the following isomerization reaction:
C 2 H 5OH( l) CH 3OCH 3 ( g )

PROBLEM 173 The standard enthalpies of formation of BH 3 (g ) and B2 H 6 (g ) are 100 kJ and 36 kJ per
mol respectively and the enthalpies of formation of B( g ) and H( g ) are 563 kJ mol 1 and 218 kJ mol 1
respectively. Determine mean B H bond enthalpies in each case. Assume terminal BH bonds have
same strengths, estimate enthalpies of the three centre B H B bonds in B2 H 6 . Which bonds would
you expect to be longer-terminal or bridged one?

24

Problems in Chemistry

PROBLEM 174 Enthalpy of combustion of C 6 H 6 (l), C 6 H12 (l) (cyclohexane) H 2 (g ) are 3268, 3920
and 289 kJ/mol respectively. If enthalpy of hydrogenation of cyclohexane is 120 kJ/mol, determine
resonance energy of benzene( l).
PROBLEM 175 Assuming that mileage of an automobile gets is directly proportional to the heat of
combustion of fuel, calculate how many times farther an automobile could be expected to go on one litre
gasoline than on 1.0 litre ethanol.
Assume gasoline to be pure n-octane ( = 0.7025 gmL1 ). Density of ethanol is 0.7893 gmL1 . H f
of ethanol and octane are 278 kJ mol 1 and 208.4 kJ mol 1 . H f of CO 2 ( g ) and H 2O( l) are
394 kJ mol 1 and 286 kJ mol 1 respectively.

PROBLEM 176 10 g of propane was burnt in air at 30C and 1.0 atm pressure. Assume air to be 21.00%
O 2 , determine volume of air required for combustion process. If all the heat produced from combustion
of 10 g of propane was transferred to 8.00 kg of water at 30C, determine final temperature of water. C P
of water is 418
. Jg 1 K 1 . Also, H f of propane, CO 2 and H 2O are: 104 kJ mol 1 , 394 kJ mol 1 and
286 kJ mol 1 respectively.

PROBLEM 177 With the following informations, determine standard state Gibbs free energy of
formation of N 2O 4 ( g ).
1
(i)
G = 86.6 kJ
N 2 ( g ) + 12 O 2 ( g ) NO( g )
2
NO( g ) + 12 O 2 ( g ) NO 2 ( g )

G = 34.82 kJ

(ii)

2NO 2 ( g ) N 2O 4 ( g )

G = 5.77 kJ

(iii)

Standard state enthalpy of formations of CO( g ) and CO 2 ( g ) are 111 kJ mol 1 and
394 kJ mol 1 respectively. Bond dissociation energies of O 2 ( g ) and C==O( g ) are 498 kJ mol 1 and 743
kJ mol 1 respectively. Supposing that there is a double bond in CO as two double bond in CO 2 ,
determine the enthalpy of combustion of CO( g ) and compare it with actual value. Also, explain the
difference in calculate and observed value of enthalpies.

PROBLEM 178

PROBLEM 179 One mole of N 2 (g ) and 3.0 mole of H 2 (g ) taken in a flask at 25C and heated to 450C.
Now pressure was applied on the gaseous mixture which results in conversion of 0.1 mole of N 2 into
NH 3 . The gases are then cooled rapidly back to 25C. Determine the net heat change in this process
given the following bond enthalpies:
N 2 ( g ) = 944 kJ mol 1 ; H 2 = 436 kJ mol 1 and average N H bond energy = 388 kJ mol 1 .
PROBLEM 180 A 150 cc portion of 0.4 NHCl is neutralized with an excess of NH 4OH in a Dewar
vessel with a resulting rise in temperature of 2.36C. If the heat capacity of Dewar and its contents after
the reaction is 1316.7 J/ C, calculate heat of neutralization.
PROBLEM 181 At 25C, the heat of solution of anhydrous CuSO 4 in a large volume of water is 66.044
kJ mol 1 , while that of CuSO 4 5H 2O is 11.495 kJ. Determine heat of reaction:
CuSO 4 ( s) + 5H 2O CuSO 4 5H 2O( s)

PROBLEM 182 The integral heats of solution at 25C, for the various solid modification of CaCl 2 in the
indicated quantities of water are shown below:

25

Problems

H1 = 4.3 kJ

(i)
(ii)

H 3 = 7.65 kJ

(iii)

H 4 = +19.06 kJ

(iv)

## Determine enthalpies of the following hydration reactions:

(a) CaCl 2 (s) + 2H 2O CaCl 2 2H 2O
(b) CaCl 2 2H 2O + 2H 2O CaCl 2 4H 2O
(c) CaCl 2 ( s) + 6H 2O CaCl 2 6H 2O

## PROBLEM 183 The enthalpy of following reactions at 25C are:

(i) Na( s) + 12 Cl 2 ( g ) NaCl( s)
H = 410.6 kJ
(ii) H 2 ( g ) + S( s) + 2O 2 ( g ) H 2SO 4 ( l)

H = 810.54 kJ

## (iii) 2Na( s) + S( s) + 2O 2 ( g ) Na 2SO 4 ( s) H = 1381.5 kJ

(iv)

1
2

H 2 ( g ) + 12 Cl 2 ( g ) HCl( g )

H = 92.21 kJ

From the above thermal data, determine enthalpy of the following reaction:
2NaCl( s) + H 2SO 4 ( l) Na 2SO 4 ( s) + 2HCl( g ).

PROBLEM 184 Given the following standard state enthalpies of reaction, calculate the standard molar
heat of formation of AgCl.
(i) Ag 2O ( s) + 2HCl( g ) 2AgCl( g ) + H 2O( l)
H = 324.4 kJ
1
(ii) 2Ag( s) + 2 O 2 ( g ) Ag 2O( s)
H = 30.56 kJ
(iii)

1
2

H 2 ( g ) + 12 Cl 2 ( g ) HCl( g )

(iv) H 2 ( g ) + 12 O 2 ( g ) H 2O( l)

H = 92.21 kJ
H = 394 kJ

PROBLEM 185 Draw Lewis structures of hypothetical molecule N 6 (g ) consisting of a six membered
ring of nitrogen atom. If its standard enthalpy of formation is 1072 kJ mol 1 , predict the most likely
structure. Given:
B.E. N 2 = 944 kJ mol 1 , N N = 163 kJ mol 1 and N == N = 409 kJ mol 1 .
PROBLEM 186 A male burns 2000 kJ of energy while jogging for 1.0 hour. If the standard heat of
combustion of a typical fat is 38 kJ g 1 and only 70% energy is available for muscular activity. What
(i)

+ H2

H = 38 kJ

(ii)

+ 2H2

H = 170 kJ

## minimum hours would he need to jog if he wished to lose 0.5 g fat?

26

Problems in Chemistry

PROBLEM 187 Strong sunshine bombards the Earth with about 1 kJ m 2s 1 . If a beaker containing
ethanol, is placed in sunlight for 10 minutes, 3.24 g of liquid was vaporized. Assuming that all the heat is
used for vaporization, not to increase temperature, determine surface area of beaker. Enthalpy of
vaporization is 42.6 kJ mol 1 .
PROBLEM 188 From the following enthalpies values, determine resonance energy of C 6 H 6 (l)
Benzene.
Also, given the resonance energy of 1,3-cyclohexadiene is 70 kJ mol 1 .

THERMODYNAMICS
PROBLEM 189 Suppose that a gas obeys the modified van der Waals equation P (Vm b) = RT and
b = 0.02 L mol 1 . If 0.5 mol of the gas is reversibly compressed from an initial volume of 2 dm 3 to a final
volume of 0.5 dm 3 , how much work is done on the system at 27C.
PROBLEM 190 One mole of a monoatomic, ideal gas confined in a 5 L piston fitted cylinder at 300 K is
heated such that its temperature increased to 400 K but at the same time gas also expanded to a volume of
8 L. Calculate change in enthalpy of the system.
PROBLEM 191 One mole of a monoatomic ideal gas confined in a 5 L, piston fitted cylinder at 300 K is
heated to 800 K as well as allowed to expand to a volume of 8 L simultaneously. Calculate change in
enthalpy of the system.
PROBLEM 192 100 g of nitrogen gas at 300 K are held by a piston under 30 atmosphere. The pressure is
suddenly released to 10 atmosphere and gas is allowed to expand adiabatically. If CV = 20.8 JK 1 mol 1 ,
calculate S System .
PROBLEM 193 Calculate entropy change when 0.5 L of an ideal gas (CV =12.6 JK 1 mol 1 ) at 300 K
and one atmosphere is allowed to expand to double its volume and simultaneously heated to 373 K.
PROBLEM 194 10 g of ice at 0C are added to 20 g water at 90C in a thermally insulated flask of
negligible heat capacity. The heat of fusion of ice is 6 kJ/mol. What is the final temperature, S System ?
C p = 75.42 JK 1 mol 1 .
PROBLEM 195 One mole of a supercooled liquid water at 10C and one atmosphere turns into ice at
10C. Calculate entropy change for the system. C p for liquid water and ice are 75.42 and
37.2 JK 1 mol 1 respectively.
PROBLEM 196 In an open beaker at 27C and one atm pressure, 100 g of zinc are caused to react with
dilute sulphuric acid. Calculate the work done by the liberated hydrogen gas assuming it to behave
ideally. What would be the work done if the reaction took place in a sealed vessel?
PROBLEM 197 A balloon is 0.5 m in diameter and contains air at 25C and 1 bar pressure. It is then
filled with air isothermally and reversibly until the pressure reaches to 5 bar. Assume that pressure is
proportional to the diameter of the balloon, calculate (a) final diameter and (b) work done in the process.

27

Problems

PROBLEM 198 One mole of an ideal gas initially at 10 bar and 300 K is allowed to expand against a
constant external pressure of 2.00 bar to a final pressure of 2 bar. During this process, the temperature of
this gas falls to 250 K. Construct a reversible path connecting this initial and final state as a combination
of reversible isothermal expansion followed by reversible adiabatic expansion so that the final state is
attained and calculate work done by the system in attaining the final state. C vm = 3/ 2 R .
PROBLEM 199 With the temperature maintained at 0C, 2 mole of an ideal gas are allowed to expand
against a piston that supports 2.0 bar pressure. The initial pressure of the gas is 10 bar and the final
pressure 2 bar.
(a) How much energy is transferred to the surrounding during the expansion?
(b) What is the change in internal energy and enthalpy of the gas?
(c) How much heat the gas has absorbed?
PROBLEM 200 A gas behaving ideally was allowed to expand reversibly and adiabatically to twice its
volume. Its initial temperature was 25C and C vm = (5 / 2) R , calculate E m and H m .
PROBLEM 201 One mole of a gas at 300 K is compressed isothermally and reversibly from an initial
volume of 10 dm 3 to a final volume of 0.2 dm 3 mol 1 . Calculate work done on the system if the equation
of state of the gas is (Vm b) P = RT with b = 0.03 dm 3 mol 3 .
PROBLEM 202 One mole of a gas at 100 K is compressed isothermally from an initial volume of
20 dm 3 to a final volume of 5 dm 3 . Calculate the work done on the system if the equation state is:

a
P + 2 Vm = RT
Vm

## where a = 0.384 m 6 Pa mol 1

PROBLEM 203 Find q,W, U and H if 2.0 g of He undergoes a reversible isobaric expansion from 20
to 40 L at 0.8 atm pressure followed by reversible isochoric heating till pressure reaches to 1.0 atm.
Depict the change of state on a P-V diagram.
PROBLEM 204 One mole of liquid water at 30C is adiabatically compressed, pressure increasing from
1.0 atm to 10.0 atm. Since, liquids and solids are rather incompressible, it is a fairly approximastion to
take V constant. Calculate q, U and H for the process. C p of H 2O( l) = 75.42 JK 1 mol 1 .
PROBLEM 205 For a perfect gas, C v = 2.5 R . 2.0 moles of this gas undergoes following change of state:
(a) A reversible isobaric expansion from 1.0 atm, 20 L to 1.0 atm, 40 L.
(b) A reversible isochoric change from 1.0 atm, 40 L to 0.5 atm, 40 L
(c) A reversible isothermal compression from 0.5 atm, 40 L to 1.0 atm, 20 L. Sketch each process on
the P-V diagram and calculate : q, W, U and H.
PROBLEM 206 A sample of an ideal gas underwent an adiabatic expansion from 298 K, 15 bar to 2.5
bar against a constant external pressure of 1.0 bar. What is the final temperature of the system and work
done by the system, assume C vm = 2.5 R?
PROBLEM 207 A gas behaves ideally and its C v is given by: C v = 21.52 + 8.2 10 3 T (all parameters
in SI unit). A sample of this gas is initially at T1 = 300 K, P1 = 10 bar and V1 = 1 L. It is allowed to expand
until P2 = 1 atm and V2 = 10 L. What are U and H for this process? Could the process be carried out
adiabatically. Calculate C p at 300 K.

28

Problems in Chemistry

PROBLEM 208 The entropy change of argon is given to a good approximation by the expression:
Sm / JK 1 mol 1 = 36.36 + 20.79 ln T
Calculate change in Gibbs free energy of one mole of argon gas if it is heated at constant pressure
from 25C to 50C.

PROBLEM 209 Initially at 300 K and 10 atm pressure, 1.0 mole of an ideal gas is allowed to expand
adiabatically against a constant pressure of 4.0 atm until equilibrium is established. Assume the gas to be
ideal with:
C p = 28.58 + 1.76 10 2 T
Calculate U , H, and S.

PROBLEM 210 An ideal gas expand against a constant external pressure of 2.0 atmosphere from 20 L to
50 L and absorb 20 kJ of energy from surrounding. What is the change in internal energy of the system?
10
atm, where V is volume of
V
gas at each stage of expansion. Further during expansion from volume 10 L to 100 L, the gas undergoes a
change in internal energy of 420 J. How much heat is absorbed by the gas during expansion?

## PROBLEM 211 A gas expands against a variable pressure given by P =

PROBLEM 212 Three moles of an ideal gas is heated at constant pressure of one atmosphere from 27C
to 127C. If C v is expressed as: C v = 30 + 14 10 3 T JK 1 mol 1 , determine W, E and q.
PROBLEM 213 One mole of an ideal gas at state A (500 K, 5.0 atm) is cooled at constant volume to
B (300 K) and then expanded isothermally and reversibly to C and finally compressed adiabatically to A.
5
Sketch the change on a P-V diagram and determine the net work done in this cyclic process. = .
3
PROBLEM 214 One mole of an ideal gas is subjected the following change of state:
Reversible
Isothermal expansion

## A(5.0 atm, 500 K) B

Isochoric cooling

Reversible

B C (300 K) A
Depicting the above mentioned change on a P-V diagram, determine the net work done in the cyclic
process. C v =1.5 R .

PROBLEM 215 One mole of an ideal gas initially at A (300 K and 5.0 bar) is heated at constant pressure
to double its volume (B). The gas is then expanded isothermally and reversibly to a new state C. The gas
is then cooled at constant pressure to another new state D (200 K) and finally compressed adiabatically
and reversibly to A. Depicting on a P-V diagram, determine the net work done in the above cyclic
process. C v =1.5 R .
PROBLEM 216 One mole of an ideal gas at A (500 K, 5.0 bar) is expanded isothermally and reversibly
to a new state B and then cooled at constant pressure to C (250 K) and finally compressed adiabatically
and reversibly to A. Depicting on a P-V diagram, determine the net work done in the cyclic process.
C v =1.5 R .

29

Problems

PROBLEM 217 One mole of an ideal gas at 500 K and 10 bar, defined by state A is allowed to expand
isothermally and does a work equal to 4200 J. Construct a combination of initial irreversible expansion
upto 2.0 bar followed by reversible expansion so that final state is reached and determine final pressure
of the gas.
PROBLEM 218 One mole of an ideal gas at 500 K and 10 bar is allowed to expand till the final pressure
falls to 1.0 atmosphere and final temperature falls to 250 K. Construct a combination of reversible path
of:
(a) initial adiabatic expansion followed by isothermal expansion so that final state is reached and
determine the total work done. C v =1.5 R .
(b) Determine the work by reversing the order of combination in (a) and compare the two work
done.
PROBLEM 219 One mole of an ideal gas at 300 K and 1.0 atmosphere is heated to 500 K and expanded
simultaneously to 36 litre. Determine H assuming heat capacity to be independent of temperature and
C v =1.5 R .
PROBLEM 220 One mole of a gas initially at 300 K is heated to 500 K. Determine the Gibbs free
energy change, G if S = 1.5 + 3 10 3 T [JK 1 mol 1 ] and C v =1.5 R .
PROBLEM 221 One mole of an ideal gas at 300 K and 1.0 atmosphere is heated as well as expanded
simultaneously to 500 K and 2.0 atmosphere. Determine S if C v = 2.5 R .
PROBLEM 222 One mole of an ideal gas is taken in a one litre sealed flask at 300 K and heated till the
pressure becomes equal to 40 atmosphere. If C v = 12 + 28 10 3 T (in SI unit), determine S.
PROBLEM 223 A gaseous reactant A forms two different product in a parallel reaction B and C as
follows:
A B ;

H = 3 kJ, S = 20 JK 1

A C ;

H = 3.6 kJ, S = 10 JK 1

Discuss the relative stability of B and C on the basis of Gibbs free energy change at 27C.

PROBLEM 224 One mole of an ideal gas contained in a sealed flask at 1.0 bar is heated from 27C to
127C. Determine G if: S (JK 1 ) = 10 +12 10 3 T .
PROBLEM 225 Two moles of NO 2 is heated at constant volume from 27C to 127C and
C p (JK 1 mol 1 ) = 28 + 31 10 3 T
Determine S.

PROBLEM 226 Two moles of an ideal gas is expanded isothermally and irreversibly at 27C from
volume V1 to 2.5 V1 and 4.17 kJ heat is absorbed from surroundines. Determine S sys , S surr and S univ .

30

Problems in Chemistry

PROBLEM 227 One mole of He(g) is mixed isothermally and reversibly with 2.0 mole of Ne(g).
Determine S.
PROBLEM 228 C vm for an ideal gas is 2.5 R and it is independent of temperature. If 2.0 moles of this gas
is subjected to the following change of state :
Reversible

## A (1.0 bar , 20 L ) B (1.0 bar, 40 L)

Isobaric heating

Isochoric cooling

Reversible
Isothermal compression

## B C (0.5 bar, 40L) A

Representing the above change of states on a P-V diagram, determine the net work done.

## PROBLEM 229 An ideal gas has

C vm = a + bT
1

where a = 25 JK mol and b = 0.03 JK mol 1 . If 3.0 moles of this gas is subjected to a
thermodynamic change of state from A (300 K, 2.0 bar) to B (500 K, 3.0 bar), determine q, W, E, H
and S.

PROBLEM 230 One mole of an ideal gas defined by state A (400 K, 5.0 bar) is heated at constant
pressure to B (500 K) and then cooled at constant volume to C. The gas is then expanded isothermally
and reversibly to a new state D (1.0 bar) and finally compressed adibatically to A. Depicting on a P-V
diagram, determine the net work done in this cyclic process. C v =1.5 R ..
PROBLEM 231 One mole of an ideal gas is subjected to the following change of state:
Reversible
Isothermal expansion

Isochoric cooling

Reversible

## C D (3.0 bar); C v =1.5 R

Depicting the above change on a P-V diagram, determine the net work done.

## PROBLEM 232 The entropy of vaporization of benzene is 85 JK 1 mol 1 .

(a) Estimate the enthalpy of vaporization of benzene at its normal boiling point of 80C.
(b) Determine the entropy change of surroundings when 100 g benzene vaporizes at its normal
boiling point.
PROBLEM 233 The entropy of vaporization of acetone is 85 JK 1 mol 1 .
(a) Estimate enthalpy of vaporization of acetone at its normal boiling point 56C.
(b) Determine entropy change of surrounding if 100 g of acetone condenses at its boiling point.
PROBLEM 234

## With the help of following reduction reactions:

TiO 2 ( s) + 2C( s) Ti( s) + 2CO( g )

(i)

TiO 2 ( s) + C( s) Ti( s) + CO 2 ( g )

(ii)

31

Problems

at

1000

K,

given

## Gf (CO) = 200 kJ mol 1 ,

Gf (CO 2 ) = 396

kJ mol 1

and

G f TiO 2 ( s) = 762 kJ mol 1 , determine which will be the predominant mode of reduction of TiO 2 ( s)
at 1000 K.

PROBLEM 235

The reaction for the production of synthetic fuel water gas from coal is:
C( gr ) + H 2O(
g ) CO( g ) + H 2 ( g )
2
3

Standard molar entropies of C( gr ), H 2O( g ), CO( g ) and H 2 ( g ) are 5.7, 70, 190 and 131 JK 1 mol 1
respectively. Also, standard enthalpy of formations of H 2O and CO are 242 and 111 kJ mol 1
respectively. Determine the standard reaction free energy of reaction at 27C. Also, predict about the
spontaneity and effect of temperature on direction of reaction.

PROBLEM 236
follows:

## The thermodynamic informations for isomerization of alkene (C 4 H 8 ) at 300 K are as

trans-2-butene

cis-2-butene

H 3C

CH 3

H 3C

C==C
H

H
C==C

G = 66 kJ mol 1
f
H = 7 kJ mol 1
f

CH 3

G = 63 kJ mol 1
f

H = 11.2 kJ mol 1
f

CH 3
C==C

CH 3
2-methylpropene
G f = + 58 kJ mol

If the temperature of the above system is increased to 400 K and equilibrium was allowed to
re-establish, mole percentage of trans-2-butene at new equilibrium was 18. Determine H and S for
the isomerization reactions below:
cis-2-butene

2-methylpropene

trans-2-butene

2-methylpropene

## PROBLEM 237 At a temperature above 65 K, decarboxylation of acetic acid, (i.e., loss of CO 2 )

becomes spontaneous. If H f of CH 3COOH, CO 2 ( g ) and CH 4 are 484.5, 394 and 74.8 kJ/mol
respectively, determine standard state entropy change ( S ) for the decarboxylation reaction. What is
the driving force for getting this reaction to proceed?
PROBLEM 238

## For the reaction:

H 2 ( g ) + CO 2 ( g )
H 2O( g ) + CO( g )
G at 2000 K is 2540 J, where partial pressures of the species are PH 2 = 0.25, PCO2 = 0.78,
PH 2O( g ) = 0.66 and PCO = 1.2 atm respectively. Determine equilibrium composition of the gaseous
mixture.

PROBLEM 239

## Consider the thermal decomposition of solid CaCO 3 as:

32

Problems in Chemistry

CaCO 3 ( s)
CaO( s) + CO 2 ( g ).
The equilibrium vapour pressure of CO 2 at 700C and 950C are 22.6 and 1830 mm of Hg. Calculate
H and S for the reaction.

PROBLEM 240 A certain reaction is spontaneous at 72C. If the enthalpy change for the reaction is
19 kJ, what is the minimum value of S for the reaction?
PROBLEM 241 The internal engine of a 1200 kg car is designed to run on octane whose enthalpy of
combustion is 5510 kJ/mol. If the car is moving up a slope, calculate the maximum height to which the
car can be driven on 2.0 gallon of the fuel. Assume the cylinder temperature is 2200C and the exit
temperature is 760C and ignore all form of friction. The mass of 1.0 gallon of fuel is 3.1 kg.
PROBLEM 242 One gram sample of oxygen undergoes free expansion from 0.75 L to 3.0 L at 298 K.
Calculate S , q, W , H and E.
PROBLEM 243 A 550 ml sample of an ideal gas at 300 K exerts 3 atm. The thermodynamic state of the
system changes in a process. In the final state, P = 3.5 atm and V = 730 mL. Calculate S and E and
H, C vm = (5 / 2) R .
PROBLEM 244 A sample of 0.0133 mole of an ideal gas, initially at 5.00 atm, expands isothermally and
reversibly from 3.00 L to 10 L. Calculate S , G and H.
PROBLEM 245 One mole of an ideal gas originally at a volume of 8.00 Lit. at 1000 K, is allowed to
expand adiabatically until final volume is 16.00 Lit. For the gas C v =1.5 R . Calculate values of S for
the process when:
(a) The expansion takes place reversibly.
(b) The expansion takes place against a constant pressure of 3.00 atm.
(c) The change in volume involves a free expansion.
PROBLEM 246 One mole of an ideal gas at 0C and 1.0 atm pressure is mixed adiabatically with one
mole of a different gas at 100C and 1.0 atm to yield a mixture. If C P for each gas is (5 / 2) R, determine
S (mixing).
PROBLEM 247

## For chloroform gas C PM is expressed as:

C PM = 24.9 + 14.8 10 2 T 9 10 5 T 2 JK 1 mol 1 .

Assuming this gas to be ideal, determine entropy change involved in heating 2.0 mole of gas from
volume 100 L at 500 K to a volume of 70 Lit. at 700 K.

PROBLEM 248

## For N 2 ( g ), entropy function as a function of temperature is expressed as:

S = 25.1 + 29.3 ln T

Determine Gibbs free energy change G of one mole of nitrogen if it is heated from 298 K to 348 K
at 2.0 atm pressure.

PROBLEM 249 One mole of an ideal gas initially at 400 K and 10 atm, is adiabatically expanded
against a constant pressure of 5.0 atm until equilibrium is attained. If CV = 18.8 + 0.021T JK 1 mol 1 ,
determine E , H and S .

Problems

33

PROBLEM 250 Molar volume of C 6 H 6 (l) is 89 c.c. at 27C and 1.0 atm pressure. Assuming the volume
to be constant, determine G for compression of 5.00 moles of liquid benzene from 1.0 atm to 100 atm.
PROBLEM 251 One mole of an ideal gas at 25C is subjected to a reversible isoentropic expansion until
final temperature reached to 75C. If the initial pressure was 1.0 atm, determine final pressure
CV = (3 / 2) R .
PROBLEM 252 A flask containing 1.00 mol of N 2 at 4.00 atm and 298 K was connected to a flask
containing 1.00 mol of N 2 gas at 2.00 bar and 298 K. The gases were allowed to mix isothermally.
Determine the entropy change for the system.
PROBLEM 253 One mole of solid iron was vaporized in an oven at 3500 K. If iron boils at 3133 K and
enthalpy of vaporization is 349 JK 1 mol 1 , determine S system , S surroundings and S universe .