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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

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

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

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

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

Problems

13

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.

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.

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 )

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

:

1,3-butadiene

= 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 + ( 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)

(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

(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

(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

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

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 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

Isochoric cooling

Reversible

Adiabatic compression

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

Isobaric heating

Isochoric cooling

Reversible

Isothermal compression

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

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

Adiabatic compression

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

(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

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 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:

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

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

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

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

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

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 .

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