CHEMICAL EQUILIBRIUM 529

The Basic Problems with Solutions

>- Problem 1. State which one is homogeneous or heterogeneous?

(a) ^Di amon d" ^graphite

(b) H 2 O (S) - H20(|)

(c) N + 3H
2NH 3(g)
2(g) 2(g)-
(d) MgC03(s)— Mg 0 ( s ) + C 0 2 ( g )
(e) P CL 3 ( G ) + CL 2 ( G ) * PCI,
•5(g)
>• Problem 2. Write eailibrium constant for the each :
(a) N204(gr 2NO 2(g)
(b) KC103(S) — KC1(S) + ( 3 / 2 ) 0 2 ( G )

(c) CaC 2 ( s ) + 5 0 2 ( g ) — 2CaC0 3 ( s ) + 2C 0 2 ( g )

(d) N 2 ( g ) + 3 H 2 ( g ) - = - 2NH,3(g)
3+
(e)Fe (aq) + SCN' (aq )' Fe(SCN) 2 + ( a q )
(F) C u S 0 4 . 5 H 2 0 ( s ) ^ = ^ C U S0 4 ( s ) + 5H 2 0 ( V )
>• Problem 3. The equilibrium constant expression for a gas reaction is :

[NH 3 ] 4 [Q 2 ] 5
KC
[N0]4[H20]6

Write the balanced chemical equation corresponding to this expression.

>- Problem 4. The equilibrium constant of the reaction; S0 3 ( g )- ss = £r S0 2 ( g ) + ' / ^ ( g ) !
is 0.20 mole'/2 litre-'7* at 1000 K. Calculate equilibrium constant for
2S02(G) + 0 2 ( G R 2SO 3(g)"
>• Problem 5. Calculate the equilibrium constant for the reaction ;
H + C0 H
2(g) 2(g)" 20(g)+ co(g)
at 1395 K, if the equilibrium constants at 1395 K for the following are
2H20(G) 2H2 + 02(G) K X = 2 . 1 X 10"
2C02(G)^=SR 2CO(G) + 0 2 ( G ) K 2 = \ A X 10"

>» Problem 6. For the reaction; N 2 ( 2 ) + 3H1 2(g)

2 — 2NH
3(g)-
At 400 K, Kp = 41 atm Find the value of Kv for each of the following
reactions at the same temperature:
(i) 2NH 3 ( g ) - N2(G) + 3 H 2 ( G ) ;

1 u N H 3(g)'.
(» ) 2 N2(g) +
2 2(g)
(iii)2N 2 ( g ) + 6H 2 ( g ) 4NH 3(g)"
>> Problem 7. Find out the value of Kc for each of the following equilibria from the
value of Kp:
-2
(a) 2NOCI ( g) 2NO ( g ) + C 12(g)
2 M ; Kd = 1.8 x IO atm at 500 K
(b) CaC0 3 ( s ) CaO ( s ) + C 0 2 ( g ) A: = 167 atm at 1073 K
530 NUMI MICAL PHYSICAL CI II MISIMY

>- Problem 8. The rate ol reversible reaction (change in concentration per second):
PtCI 4 2 " + H 2 0 Pt(H 2 0)CI 3 ~ + C P ; was observed at 0.3 ionic
strength at 25 °C and noticed that

A[? 4 ]= 3 9 x 10 5 ptcl 2 -3
a/' ~ t 4 l - 2 . i x IO [Pt(H20)Cl3"][Cl~]
Calculate:
(a) Rate constant for forward and backward reaction.
(b) The equilibrium constant for the complexation of fourth Cl~ at 0.3
ionic strength.
>» Problem 9. Write a stoichiometric equation for the reaction between A2 and C
whose mechanism is given below. Determine the value of equilibrium
constant for thefirststep. Write a rate law equation for the overall
reaction in terms of its initial reactants.

Kx = 1 0 ' V and K2 = l O ^ A r y 1
1
(i) A2 2A
2
1
(ii) A +C > AC lO^AT's"
> - Problem 10. Equilibrium constant, K^. for the reaction, N 2 ( g ) + 3 H 2 ( g ) ^ = ^ 2 N H 3 ( g ) ;
2 -2
at 500 K is 0.061 litre mole . At a particular time, the analysis shows
that composition of the reaction mixture is 3.00 mol litre . N 2 , 2.00
1
mol litre" H 2 , and 0.500 mol litre" N H 3 . Is the reaction at equilibrium?
If not, in which direction does the reaction tend to proceed to reach
equilibrium?
>• Problem 11. Which of the following reactions will get affected by increase of
pressure? Also mention, whether change will cause the reaction to go
into the right or left direction?
CH + 2S CS + 2H
(0 4(g) 2(g) 2(g) 2S(g)
(ii) C 0 2 ( g ) + C ( s ) — 2CO(g)
(iii)4NH 3(g) + 5 0 2 ( g ) — 4NO(g) + 6H20(g)
(iv)C 2 H 4 ( g ) + H 2 ( g ) C2H6(g)
>• Problem 12. In which case does the reaction go farthest to completion :
10 10
K= 1; K= 10 ; K= IO" and why?
J iS
>• Problem 13. The equilibrium constant Kc for A^ = - B^ is 1.1. Which gas has a
molar concentration greater than 1?
>• Problem 14. Nitric oxide reacts with bromine and gives nitrosyl-bromide as per
reaction given below:
2 N O ( g ) + Br 2 ( g ) — 2NOBr(g)
WTien 0.087 mole of N O and 0.0437 mole of Br 2 are mixed is a closed
container at constant temperature, 0.0518 mole of N O B r is obtained
at equilibrium. Calculate equilibrium amount of nitric oxide and
bromine.
CIII MICAI EQUILIBRIUM 531

>- Problem 15. At 700 K equilibrium constant for the reaction;

H + ! 2HI
2(g) 2(g) (g)
-1
is 54.8. If 0.5 mol litre of HI ( g ) is present at equilibrium at 700 K ,
what are the concentrations of H 2 ( g ) and I2(g) assuming that w e initially
started with H I ^ and allowed it to reach equilibrium at 700 K .
• Problem 16. Bromine monochloride, BrCl, decomposes into bromine and chlorine
and reaches the equilibrium.
2BrCl ( g) Br 2 ( g ) + Cl 2 ( g )
for which Kc = 32 at 500 K . If initially pure BrCl is present at a
concentration of 3.30 * 10 - 3 mol litre-1; what is its molar concentration
in the mixture at equilibrium?
>• Problem 17. 60 m L of H 2 and 42 m L of I 2 are heated in a closed vessel. At
equilibrium the vessel contains 28 m L of HI. Calculate degree of
dissociation of HI.
• I'roblcm 18. The reaction 2HI H 2 +1 2 , at equilibrium contained 7.8 g, 203.2
g and 1638.4 g of H 2 ,1 2 and HI, respectively. Calculate K c .
• Problem 19. In the dissociation of HI, 2 0 % of HI is dissociated at equilibrium.
Calculate Kp for
HI ,/ jH + ,/2l
(g) 2(g) 2(g)
• Problem 20. If a mixture of 3 moles of H 2 and one mole of N 2 is completely
converted into N H 3 . What would be the ratio of the initial and final
volume at same temperature and pressure?
• Problem 21. At a certain temperature and a total pressure of 10s Pa, iodine vapour
contains 4 0 % by volume of I atoms; Calculate Kp for the equilibrium.
! 2I
2(g) (g)
• Problem 22. Reaction between nitrogen and oxygen takes place as following :
2N2(g) + 0 2 — 2N20(g)
If a mixture of 0.482 mole N 2 and 0.933 mole of 0 2 is placed in a
reaction vessel of volume 10 litre and allowed to form N 2 0 at a
temperature for which Kc = 2.0 * 10-37litre mole - 1 . Determine the
composition of equilibrium mixture.
>• Problem 23. On e mole of H 2 0 and one mole of C O are taken in a 10 litre vessel
and heated to 725 K . At equilibrium 40 per cent of water (by mass)
reacts with carbon monoxide according to the equation;
H
2°(g) + C 0 ( g ) — H2(g) + C02(g)
Calculate the equilibrium constant for the reaction.
• Problem 24. A sample of pure PC1 5 was introduced into an evacuated vessel at
473 K . After equilibrium was attained, concentration of PC1< was
found to be 0.5 x 10"1 mol litre-1. If value of A:c is 8.3 * 10~3mole
litre-1 What are the concentrations of PCI3 and Cl 2 at equilibrium?
>• Problem 25. The equilibrium constant for the following reactions is 1.6 * 10 5 at
1024 K, H 2 ( g ) + Br 2 ( g ) — 2HBr ( g )
532 NUMERICAL PHYSICAL CHI MIS I HY

Find the equilibrium pressure of all gases if 10.0 bar of HBr is

introduced into a sealed container at 1024 K.
>- Problem 26. At 1127 K and 1 atm pressure, a gaseous mixture of CO and C 0 2 in
equilibrium with solid carbon has 90.55% CO by mass;
CM + co2(g) — 2co(g)
Calculate Kc for the reaction at the above temperature.
>- Problem 27. The ester, ethyl acetate is formed by the reaction between ethanol and
acetic acid and equilibrium is represented as :
CH 3 COOH (1) + C 2 H 5 OH (1) — CH 3 COOC 2 H 5 ( a q ) + H 2 0 ( 1 )
(a) Write the concentration ratio (reaction quotient), Q e , for this
reaction. Note that water is not in excess and is not a solvent in
this reaction.
(b) At 293 K, if one starts with 1.00 mole of acetic acid and 0.180 of
ethanol, there is 0.171 mole of ethyl acetate in the final equilibrium
mixture. Calculate the equilibrium constant.
(c) Starting with 0.500 mole of ethanol and 1.000 mole of acetic acid
and maintaining it at 293 K, 0.214 mole of ethyl acetate is found
after some time. Has equilibrium been reached?
> Problem 28. Kc for CO (g) + H 2 0 ( g ) C0 2 ( g ) + H 2 (g ) at 986°C is 0.63. A mixture
of 1 mole H 2 0( g ) and 3 moles CO (g l is allowed to react to come to an
equilibrium. The equilibrium pressure is 2.0 atm.
(a) How many moles of H 2 are present at equilibrium?
(b) Calculate partial pressure of each gas at equilibrium.
> Problem 29. When C 2 H 5 0 H and CH 3 COOH are mixed in equivalent proportion,
equilibrium is reached when 2/3 of acid and alcohol are used. How
much ester will be present when 2 g molecule of acid were to react
with 2 g molecule of alcohol.
>• Problem 30, When (a) d-glucose is dissolved in water, it undergoes a partial
conversion to (P) af-glucose to exhibit mutarotation. This conversion
stops when 63.6% of glucose is in (i-form. Assuming that equilibrium
has been attained, calculate Kc for mutarotation.
>- Problem 31. Determine the concentration of C 0 2 which will be in equilibrium with
2.5 x IO"2 mol litre -1 of CO at 100°C for the reaction;
FeO (s) + CO (g) — Fe (s) + C 0 2 ( g ) ; Kc = 5.0
>• Problem 32. For the gaseous reaction; 2 N0 2 N 2 0 4 , calculate AG° and Kp for
the reaction at 25°C. Given G / N 2 o 4 and G / N 0 2 are 97.82 and 51.30
kJ respectively. Also calculate AG0 and Kp for reverse reaction.

> Problem 33. AG° for ^ N 2 + \ H 2 NH 3 is -16.5 kJ mol -1 at 25°C. Find out
Kp for the reaction. Also report Kp and AG° for :
N 2 + 3H 2 2NH 3 at 25°C
CIII MICAI EQUILIBRIUM 533

• I'roblcm 34. Calculate the values of AE° and A H° for the reaction :
2Aig) + B(g) A2B($) for which Kp = 1.0 x i o - 1 0 a tm - 2 and
A S = 5 J K - 1 and r = 3 0 0 K .
>• I'roblcm 35. Derive the best conditions for dissociation of N H 3 ; Given
2 N H 3 ^ = ^ N 2 + 3H 2 ; AH= +91.94 kJ
> I'roblcm 36. Derive the best condition for the formation of N H 3 ; Given,
N 2 + 3H2 2NH3; AH= -91.94 kJ
> Problem 37. Kc for the reaction; A + B P + Q, is 2.0 x 10~2 at 25°C and it is
-1
2.0 x 10 at 50°C. Predict whether the forward reaction is exothermic
or endothermic.
• I'nilili'iii ih. Ina gaseous reaction, A ^ + B ^ ^ ^ C ( g ( . Predict the effect of addition
of inert gas if addition is made at (a) constant volume, (b) constant
pressure.
>• Problem 39. In a gaseous reaction; A ^ + 5 ( g ) C ( g ) + D ( g ) , the increase in
temperature causes the change in the concentrations of A, B, C and D.
The concentrations of C and D also change on addition of some amount
of A. Does the value of K change in either of the two situations?
>- Problem 40. 100 g of NaCl is stirred in 100 m L o f water at 20°C till the equilibrium
is attained :
(a) H o w mu c h NaCl goes into the solution and h o w mu c h of it is left
undissolved at equilibrium? The solubility of NaC l at 20°C is 6.15
mol/litre.
(b) What will be the amount of NaCl left undissolved if the solution is
diluted to 200 m L ?
> Problem 41. Calculate the concentration of C 0 2 in a soft drink that is bottled with
a partial pressure of C 0 2 of 4.0 atm over the liquid at 25°C. The
Henry's law constant for C 0 2 in water is 3.1 x 10""2 mol/litre-atm at
this temperature.
• Problem 42. Calculate the concentration of C 0 2 in a soft drink bottle after the
bottle is opened and sits at 25°C under a C 0 2 partial pressure of
4 -2
3.0 x 10" atm. Henry's law constant for C 0 2 in water is 3.1 * IO
mol/litre-atm at this temperature.
534 NUMERICAL PHYSICAL CHEMISTRY

Answers

1. (c) and (e) homogeneous, (a), (b) and (d) heterogeneous ;

2. See solution ; 3. 4NO + 6H20 ^ ^ 4NH3 + 502 ;
4. 25 mol
-1
litre ;
+1
5. 2.58 ; -tn
3 4
6. (i) 0.024, (ii) 6.4, (iii) 1.681 * 10 ; 7. (a) 4.38 * 10" , (b) 1.90 ;
8. 53.85; 9. K{C\[A2f;
10. See solution;
11. (i) N o change, (ii) left direction, (iii) left direction, (iv) right direction ;
12. See solution; 13. See solution;
14. N O = 0.0352 mole, Br 2 = 0.0178 mole;
-1 -1
15. 0.068 mol litre ; 16. 3 x l O ^ m o l litre ;
17. 71.9%; 18. 0.019;
19. 0.125;- 20. 2;
4
21. 2.67 x 10 Pa;
-1 -1
22. N 2 = 0.0482 mol litre , 0 2 = 0.0933 mol litre ,
-21 1
N 2 0 = 6.6 x 10 mol litre" ;
2
23. 0.44; 24. [PC13] = [Cl2] = 2.037 x 10" ;
25. H 2 = Br 2 = 0.025 bar, H B r = 9.95 bar;
1
26. 0.156 mol litre" ;
27. (a) See solution, (b) 3.92, (c) No;
28. (a) 0.681, (b) C 0 2 = H 2 = 0.34 atm, C O = 1.16 atm, H 2 0 = 0.16 atm;
29. 1.33; 30. 1.747;
2 1
31. 12.5 x 10" mol litre" ;
32. -4.78 kJ, Kp = 6.88, +4.78 kJ, Kp = 0.145 ;
1 5 2 1
33. 779.41 atm" ,6.07 x 10 atm" , -32.998 kJ mol" ;
34. 63.93 kJ; 35. See solution;
36. See solution; 37. Endothermic;
38. (a) no change, (b) backward direction;
39. See solution; 40. (a)36g, 64 g, (b)28g;
1 - 1
41. 0.12 mol litre" ; 42. 9.3 x 10 * mol litre" .