- -~-~ - \. n / VJ 1.1...1.\.,., .)J~l~lll - - J.UJ. • .)..1 J. .

3
*Q.32. Three moles of an ideal gas are expanded isothermally from a volume of 300 cm to 2.5 L at l
against a pressure of 1.9 atm. Calculate the work done in L.atm and joules.
Solution:
Given: Initial volume (V 1) = 300 cm3 = 300 x 10-3 L = 0.3 L, Final volume (V2) = 2.5 L ,
Temperature (T) = 300 K, Pressure (P) = 1.9 atm
To find.: The work done (W) in L.atm and joules
Formula: W =-P~V
Calculation: From formula,
W =-P~V
W = -1.9(2.5 .- 0.3) = -1.9 x 2.2 = - 4.18 L.atm
Now, 1 L.atm = 101.3 J
So -4.18 L.atm = - 4.18 x 101.3 J = -423.4 J
W = -423.4 J.
Ans: The work done (W) = --4.18 L.atm = - 423.4 J.
_ . dul
SIii. )II Sd.: Pafat:Gtelllistiy::f
- 5
*Q-l6. One mole of an ideal gas is compressed from 500 cm3 against a constant pressure of 1·216 x lO Pa.
The work invoh'ed in the process is 36.50 J. Calculate the final volume.
.Sobaian·:.
Gn·en: Initial volume (V 1) = 500 cm3 = 0.5 L, Pressure (P) . 1.216 x 105 Pa= 1.2 atm,
Work (W) = 36.50 J = 0.36 L.atm
To find: Final volume (V2)
Formula: W=-P~V
Calculation: From formula,
W =-P~V
0.36 = -1.2 x (V2 - 0.5)
0.3 6 = -(V2 - 0.5)
1.2
· 0.3 = -V2 + 0.5
•• V2 = 0.2 L = 200 cm 3
Ans: The final volume (V 2) = 200 cm 3•
 , · ~1 -·" " JLV n• · . thermally and reversibly from a
*Q.38. Calculate the maximum work when 24 g of oxygen are expanded iso
pressure of 1.6 x 105 Pa to 100 kPa at 298 K.
Solution:
Given: Mass (m) = 24 g, Initial pressure (P 1) = 1.6 x 105 Pa, ·
Final pressure (Pi) = 100 kPa = 100 x 103 Pa= 105 Pa, Temperature (T) = 298 K
To find: Maximum work (W max)

Formula: W max= -2.303nRT log10.!J_

P2
\
I
I

Calculation: n = 24 = 0.75 moles, R = 8.314 J K- 1 mor 1 \ \

32
From formula,
. pl
\
W max = -2.303nRT log10-
P2
1.6 X 105
= -2.303 x 0.75x 8.314 x 298 x log 105 = -2.303 x 0.75x 8.314 x 298 x log 1.6
= - 4279.39 x log 1.6 = - 4279.39 x 0.2041 = - 873.4 J
Ans: The maximum work (W max)= - 873.4 J.
 Chapter 03~t.,nem•w• , " "' , or - - ,

Ene,r pt1c.s

lt•IN 11r1, 1\011111rcNNcd IN11t,hcrmally uncl rtvc"lt,ly tr, a volurn1o ,,f 2 L , TIU,
·rtiri•t' 111olt•N of llll hhi11l
·~>..''\,,,,.,k ,101u' IN 2.'>HJ k,1 "' 2'2 v( '. Culculntc the lnlthtl volu,nc ,,r tht g,a~.

NutHhcr of 1nolos (o) :\ 1uoluH, l"inal volume (V't ) 2 L,

l\~nxin,Hn, wol'k (Wnu,") 2.98J kJ 2.983 / 1(/~J, 'l'cmp~raturc n )-' 22 '.1C 295 K
tnitinl Vt)h1111~(V 1)
/ 11 fi,,J:
V•./ 11 u,, · 2.JOJ x nRT log ~
f°1'fl"''"': v1
Fron, forrnuln.
W111,. , = - 2.303 x nRT log ~
I

1 . 2 [ ·: R == 8.314 J K- 1 mor 1]
2.983 x 1o· = - 2.303 x 3 x 8.314 x 295 log V
I

2. 983
----= I 2
og-
X 103 -o.176==log v2I
16,945.22 v1
Taking antilog on both sides,
2
Antilog [-0.176] - V
I

2
o.6668 = y
I

y = 2 = 2.999 L ~ 3L
,0.6_668
l

Ans: The initial vol;me (V 1) == 3 L.

 ~4} "" 1 R ... 10 : ka. of ft#fn)Rt-n I• ~•P•nd~d. l,nthrrm•lly •nd r~e r•ihty st ' - K
- frfJWI 15 · 15 ' , ... s .-: ~
wltC"II tltf' ·• orl done- I, found to he - 17.JJ k.J . Find the Onal prt~tur ~.

'I.fa,, of mtm ic-n - 2.1< IO ' l.:g. Temperature (Tl - 1fl() K

y _ , Hi' J
ln a ,al pre_i..~ure {P .J == 15. 15 x JO ( Nm· :. \.Vork done cw~ . , - - t, J3 kJ = -l , 33
• F ina.I flTe'~~UfT ( P: )

\ \ tU,I~ - - 2 .JOJ nRT log ~

P,...

Numher of moles (nJ .::. -J -8 x I·o-J x I 0 = I mole

3

28
From formu la.
p
" • ..&A • :!.JOJnRT log -.!..
P,
15.15 x l0~
- l" J J " 10 1 == - 2.303 x I " 8.3 14 x 300 log P,

~ l5 . l5 xt 0~
I .. l J"', JO·'= 5.744 ' lO· log - -p'-
•w I - -

17 33 1515 ~ 10·
lo~
5.744 p
1.5 15 x Hf
3.01 " log
p
.
 Std.

on both sides,
15. }5 X }0 5
•
• •
1040=
-Is.1sp x ·10 5

• 2
• •
p2 = ~ 5. J 5 X J 05
Ans: 1040 = 1456.7 Nm-2
The final Pressure (P2) ==
1456.7 -2
 *Q.59. A sample of gas absorbs 4000 kJ of heat. \
i. If volume remains constant, what is AU? 1 the surroundings does 2000 kJ of
ii. Suppose that in addition to absorption of heat by the samp e, \
work on the sample, what is AU? . . a ainst atmospheric pressure and
iii. Suppose that as the original sample absorbs heat, It expands g
does 600 kJ of work on its surroundings. What is AU?
Solution:
Given: q = 4000 kJ \
To find: .1U
Formula: L1U = q + W
Calculation: i. At constant volume, ~H = ~U
So, ~U = + 4000 kJ
..
11. Sample absorbs 4000 kJ heat and the ·surroundings does 2000 kJ of work on sample .
L1U = q + W
So, ~U = 4000 + 2000 = + 6000 kJ
n1. Sample absorbs 4000 kJ heat, expands against atmospheric pressure and does 600 kJ of work
on its surroundings.
~U=q +W
~U = 4000 - 600 = + 3400 kJ
Ans: 1. ~u = + 4000 kJ ii. ~u = + 6000 kJ 111. ~U =+ 3400 kJ
 - - F
....... . ._ ___
__

Ener1etics

1ml■iiHlit .,.
~ ·
~Q 71. Calculate th e work done in each of the following reactions. State whether work i.s done on
the
· system or by the system.
i. The oxidation of one mole of so 2 at 50 oc.
2S02(g) + 02cgl ~ 2S0 3<gl
u. Decomposition of 2 moles of NH 4NO 3 at 100 °C.
NH4NOJ(s) ~ N20<g) + 2H 20<g>

Oxidation of one mole of SO 2 , T = 50 °C = 323 K

1.

ii. Decomposition of 2 moles ofNH4NO 3 , T = 100 °C = 373 K

Tofind: Work done and to determine whether work is done on the system or by the system.
Forrnula: W = -~nRT
Calculation: i. 2S02cg) + 02(g) ~ 2S0 3(g)
1 mole of S02 will react with 0.5 mole of 0 2 to give l mole of S03.
W = -~n.RT = -RT(n2 - n1) .
W = - 8.314 X 323(1-1.5) = - 8.3 \4 X 323 X (-0.5)
W = 1342.7 J
As W is positive, work is done on the system.
11. NH4N03(s) > N20cg) + 2H20(g)
2 moles of NH4N03 (s) gives 2 moles of N 20cg) and 4 moles of H20 (g)•
So, ~n = (6 - 0) = 6 · {n 1 = 0 as NH4N0 3 is in solid state)
W=-~n.RT
=-6 X 8.314 X 373 =-}8606.75 J
W = -18.61 kJ
As W is negative, work is done by the systen1.
Ans: i. Work done (W) = 1342.7 J.
11. Work done (W) = -18.61 kJ.
Std~ XU Sci. : Perfect Chemistry - I

*Q. 73. The enthalpy change for the reaction: C2H4 (g) + H2 (g) ► C2H6 <g> Calculate the pressure
is - 620 J when 100 mL of ethylene and 100 mL of H2 react at l atm pressure.
volume work and AU.
Solution:
. - 0 2 L Pressure (P) == l atm
Given: Enthalpy change (~H) = -620 J, Initial volume (V 1) = 200 mL - · ' . t'on
. . (0AU) for the given reac 1
To find: Pressure-volume \Vork (W) and change 1n internal energy
Formula: W = -P~V
Calculation: From formula,
W = - p ~V = - l x (0 .1 - O.2) = - l x - O.1 = O.1 L. atm = 0. l x l O1. 33 J = + 10.13 J
W -P~V
-
10.13= -P~V
P~V = -10.13 J
~H - ~U+P~V
~H - -620 J
... ~u - MI-PAV I () I
-620-(-10.13) = - 620 + 10.13 = -609.9 J
-
Ans: Pressure-volume work (W) = 10.13 J and ~U = -609.9 J.
- - -- - 1
/
~ • • a
- I
•Q.114, Calcuhlaf~elslta~dard enthalpy of the reaction Fe2O3hl + 3COtil --,.,) 2Fe\s) + 3C02(g)
From t e o owing data:
/\rH° (Fe203) = - 824.2 kJ m 0 1- 1 , i\fHo (CO) = _ 1 to.S kJ mor', ArH 0 (CO 2) = - 393.5 kJ mor'
Solution:
Given: L\rH° (Fei0 3) = - 824 .2 kJ /mol. Q 1H 0 (CO) = - 110.5 kJ /mol , ilrH 0 (C O 2) = - 393.S \d /mo\
To find: Standard enthalpy of the gi\. en reaction (£\H0 )
O 0
formula: L\H = LL\rH (products) - ~ Q1l{" ( rcac tant,;; )
Calculation :
Standard enthalpy of reaction (.'\l\ ) ~ ~ ,H° (products) - LL\rH0 (reactants)
= [2 x ~ rl-I O (Fe) + 3 x ~ .,I t O ( t ·t) ~ l \ • l \ x ~ t l lO (Fe 20 3) + 3 x ~ rH O (CO)}
== [2 X O + 3 x (- 393.5)] - l- 824.2 r 3 x ( - \ 10.S)l
= [0 + (- 1180.5)] - [- 824 .2 + (3 x - l lO.S)l -= - 1 \80.5 + 824.2 + 33\ .5 == - 24.8 kJ
Ans: The standard enthalpy of the given reaction is -24.8 kJ.
 •.1. J JJ:::: - I 1>5 fJ.5 ~ 0
en reaction is••-24.8
- 6" k.J. - - • ·
\124 2 j j ' ). = - L-4.'5 ¥..,J
•v.u., . ..........,uate the standard enthalpy or formation of C2H6 frorn the foJtowing data:
2C i ~ 1 + 702<t> -._. 4Co2<g1+ 6lf2011i, i\Ho == -3119 kJ
Solatwn:
liffo(C02) == -393.5 kJ tnor-1, i\rlfo(H20) == -285.8 kJ mor'.

Standard enthalpy of reaction (LlH 0 ) = -3119 kJ.

.0 .find:
T
0

LltH (CO2) = -393_5 kJ!mof, Llrff 0 (H 2O) = -285.8 kJ/mol.

Formula: Standard enthalpy of formation of ½Hi; (LlrH 0 )
Calculation: LlH 0 = UtH0 (products) - UrH0 (reactants)
Standard enthalpy is given by the fonnula,
LlW = UtH 0
(products)- UrH0 (reactants)
0
- 3] 19 = (4 X .'lrff (CO2) + 6 )( 6rff0 (H20)] - (2 X i:\rff 0 (C2H,;) -'- X L'.rff~<O~)] .
7
- (4 x (-393.5)
0
+ 6 x (-285.8)] - [2 x 6rH 0 (C2Ifi;)] fr itself is zero. l
[6rff (0 ) = o, as the standard enthalpy of formation of an element om
2
 / r ,,' I •J

Std. ,cu sc1.: Perfect Chemtstry/": I·. ,

- 3119 = - 1574 - 1714.8 - 2 x LirH 0 (C 2H 6 )
- 3 1 19 = - 3288.8 - 2 x Lirl-1° (C 2 H6)
169.8 = - 2 x LirH 0 (C2H6)
- 84.9 == ~rH 0 (C2H6)
...
LlrH 0 (C2Fl6) = -84.9 kJ mol- 1 .
• ,. ~tandard enthalpy of formation of C2H6<s> is -84.9 kJ mor'.
ips: nc'-HV11Vl1Hdll011 0 f02 5 ., ' - ~ '"'/" V, ,t_,J - - /...Jhd
I' moles of water is -75 kJ.
•

«Q.102. How much heat is evolved whe 12 f . d. t the following reaction,

4CO + 2NO -~ n go CO reacts with N0 2 accor 1ng o
(g) 2 (g) ➔ 4 co 2 (g) + N2 () AH 0 = -1198 kJ?
50/ution: g' •

Given: ~H 0 = -l l 98 kJ, Mass of CO= 12 g

To find: Heat ev_olved when 12g of CO reacts with N02 · ·
Calculation: According to the given reaction, 1198 kJ of heat is evolved when 4 moles of CO react with N02.
So heat evolved per mole is 1198 = 299.5 kJ.
4
Mass of CO 12
Number of moles of C O = - - - - - - = - = 0.4285 moles
Molar mass of CO 28
So, heat evolved when 0.4285 moles of CO reacts= 0.4285 x 299.5 = 128.3 kJ
Ans: The heat evolved when 12 g of CO reacts wi.th NO 2 is 128.3 kJ. ----------·-·-----------------·---
 *Q. 104. 38.55 kJ of heat is absorbed when 6.0 g of 0 2 react with CIF according to the reaction,
2CIF(gJ + 02(g> ➔ C)iO<g> + OF 2 <g>
\Vhat is the standard enthalpy of the reaction?
Solution:
Given: Heat absorbed= 38.55 kJ, Mass of 0 2 = 6.0 g
To find: Standard entha]py of the given reaction
Mass of O 2 6
Calculation: Number of moles of 0 2 = = - = 0.1875
Molar mass of 0 2 32
38.55 kJ heat is absorbed when 0.1875 moles ofO 2 react with CIF.
38 55
Heat absorbed for 1 mole = · = 205.6 kJ
0.1875
From the reaction, 2 moles of ClF react with 1 mole of 0 2 •
So, standard enthalpy of reaction is +205.6 kJ.
Ans: Standard enthalpy of the given reaction is +205.6 kJ.
 ·· v •11 il.
c_·alcuJate LiHo . - --~ --~ -££~ ~~ +HO
From th • of the reaction: CH4(g) + Oi(g) ➔ CH2 0(g) 2 (g)
- - - e follow1ng data:
.Bond , ------------------------------------------ 1

AHOllr,J 1-1 _ C-H ! 0 = O I C = O i 0-H I

--------- +---·--·---·------•✓----- ··--- - -------i---·-----·-------1
- ---- ~!:!!~--- 414 ! 499 f 745 I 464 I
-----~---------L·---------~---------j .•~··---~----------l
Solution: ---- - - - - - ----- - I --·~

Given: MI (C- H) = 414 kl mo1- 1, i1H 0 (0 = 0) = 499 kJ mo1- 1, ~H 0 (C = 0) = 745 kJ mol- 1 ,

0

.1H 0 (0 - H) = 464 kl mol- 1

fa 7
To _find: ~H0 of the reaction.
fo nntila: ~H 0 = L~H 0 (reactant bonds) - I~H 0 (product bonds)
('alcHlation: ~H0 == L~H0 (reactant bonds) - I~H 0 (product bonds)
= l4~H0 (C - H) + &H 0 (0 = O)] - [2 ~H 0 (C - H) + ~H 0 (C == 0 ) + 2Llli 0 (0 - I
= 2~H (C - H) + &H (0 = 0) - ~H (C = 0) - 2 ~H (0 - H)
0 0 0 0

= (2 x 414) + 499- 745 -(2 x 464) = -346 kJ

..\ns: ~H 0 for the given reaction is - 346 kJ . .
-, ,tQ.1 t 9. L aicuiate <-=- C l bond enthalpy from the following data:
CH3Cl(g) + Cl2(g) ► CH2Cl2(g) + HCl 'AH 0 = -104 kJ.
----- -- ---R --~----...., ----- --- (g)
Bond
__
C-n-T _ - --1---.•-- ------ --I
- . _ ___ ___ _____ _1 Cl Cl , H-Cl :
AH0 /kJ mol-'"'1 ._ ____
414 1
1 243 ----1\~--------------~\
____ ___J____________ 431 I
---- --·- .. - - ... - -- --- - - _______ J

OR
Calculate C-Cl bond enthalpy from the following reaction:
CH3C1<_g) + Ch(g) ► CH2Cl2(g) + HCl(g); AH0 = -104 kJ
If C-H, Cl-Cl and H-Cl bond enthalpies are 414,243 and 431 kJ mor 1 respectively. {Mar 16\
Solution:
Given: Llli 0 . for the given reaction~ -104 kJ
To find: ~H 0 (C - Cl)
Formula: ~H 0 = L~H 0 (reactant bonds) - L~H0 (product bonds)
Calculation:~H0 = L~H0 (reactant bonds) - L.AH0 (product bonds) [1/:z Mark]
[36.H0 (C-H) + ~H0 (C-Cl) + AH0 (Cl-Cl)1-l2AH0 (C-H) + 2AH0 (C-C\) + ~H0 (H-C\)1
[1 Mark]
~H 0 (C-H) - ~H 0 (C-Cl) + AH 0 (Cl-Cl) - AH0 (H-Cl)
-104 = 414 - ~H 0 (C-Cl) + 243 - 431 [½ Mark]
6.H0 (C - Cl) = 414 + 104 + 243 - 431 = 330 kJ mor 1 [l Mark}
Ans: C - Cl bond enthalpy is 330 kJ mor 1 •
 I .
*Q.121. Gh·en the following equation, calculate the standard enthalpy of the reaction,
3
2Fe(s) + 2 02(g) ► Fe20J(s) i\ffO =?
i. 2A~s> + Fe20 J(s> -~► 2Fe(s) + Al 2 O 3(s) AHO = -847.6 kJ
,
3
ii. 2A1<s) + 2 02(g) ► AliOJ(s) ' AHO = -1670 kJ
Solution:
Given: Given equations are,
~H 0 = -847.6 kJ .... ( i)
2Alcs) + Fe203cs) > 2Fecs) + Ah03cs) ,
3
~H = -1670 kJ .... ( ii)
2Al(s) + - 02(g) ) Ah03(s) ' 0

2
t •
To find: Standard enthalpy of the given reaction
Calculation: Reversing equation (i),
2F ecs) + Ah03cs> > 2Alcs) + Fe2O 3 cs) , ~H 0 = 84 7 .6 kJ .... (iii)
Adding equation (ii) to equation (iii),
2Fecs) + Ah03cs) > 2Alcs) + Fe203.(s), ~H 0 = 847 .6 kJ
3
2Alcs> + 2 02cg> --> Ali03(s), ~H 0 = -1670 kJ
3
2Fecs> + 2 02cg> --> Fe203(s), ~H 0 = 847.6 + (-1670) = -822.4 kJ
Ans: The standard enthalpy of the given reaction is -822.4 kJ.
 111111 1

*Q.125. Given the following equations and AH 0 values at 25 °C,

i. Si(s) + 02(g) ) Si02(s), Aff 0 = -911 kJ

ii. 2C(graphite) + 02(g) ► 2CO(g), AH 0 = -22_1 kJ

iii. Si(s) + C(graphite) ► SiC(s), AH 0 = -65.3 kJ
Calculate AH 0 for the following reaction,
Si02(s) + 3C(graphite) ) SiC(s) + 2CO(g)•
Solution:
Given: Given equations are,
Sics> + 02cg) > Si02cs> ~H 0 = -911 kJ , .... (i)
2C(graphite) + 02(g) . ) 2CO(g) ~H 0 = -221 kJ .... (ii)
Sics) + C(graphite) ) SiC(s) ~H 0 = -65.3 kJ . . . . (iii)
To find: The standard enthalpy of the given reaction
Calculation: Reversing equation (i),
Si02(s) ) Si(s) + 02(g) ~H 0 = 911 kJ .... (iv)
Adding equations (iv), (ii) and (ii9i
Si02cs> ➔~, + <Yicg), ~H 0 = 911 kJ
~ ~~ l e ) +~ g) > 2COcg>, ~H 0 = -221 kJ
Ki + ((graphite) ) SiC c~), ~H 0 = -65.3 kJ
•
Si02(s) + 3Ccgraphite) > SiC(s)+2CO(g),~H 0 = 911 +(-221)+(-65.3)= +624.7kJ
Ans: The standard enthalpy (~H 0 ) for the given reaction is +624. 7 kJ.
 *Q.126. Gh·eo the following eq1111tions and L\H 0 values at 25 oc.
. 0 AHO - +14 4 kJ
I. lH.iBO.it•ql >B20.1(s) + JH2 (/)• uo -- o.02 kJ
ii. HJBO3<:1q> >HB02,aq> + H20(l), A
ill. H2B407(s) ) 2B203 (s) + H20(/), Aff :::: 17.J kJ
0

Calculate AH 0 for the following reaction:

H2B407(s) + H20(/) ) 4HB02(aq)
Solution:
Given: Given equations are,
2H3BO3(aq) ) B2O3(s) + 3H2O(/), .1H 0 = +14.4 kl .... ( i)
H3BO3(aq) ) HBO2(aq) + H2O(l), .1H 0 = - 0.02 kl .... (ii)
H2B4O7 (s) ) 2B2O3 (s) + H2O({), .1H 0 = 17 .3 kl .... (iii)
To find· The standard enthalpy of the given reaction (.1H 0 )
Calculation: Reversing equation (i) and multiplying by 2,
2B2O3(s) + 6H20(l) ) 4H3BO3(aq) .1H 0 = -28.8 kJ .... (iv)
Multiplying equation (ii) by 4,
4H3BO3(aq) ) 4HBO2(aq) + 4H2O(l), .1H 0 = -0.08 kJ .... (V)
Adding equation (iv), (v) and (iii),
2B2O3(s) + 6H2O(l) ) 4H3BO3(aq), .1H 0 = -28.8 kJ
4H3BO3(aq) ) 4HBO2(aq) + 4H2O(I), .1H 0 = -0.08 kJ
H2B401(s) ) ' 2B2O3(s) + H2O(i), .1H 0 = 17 .3 kl
H2B4O1(s) + H2O(/) ) 4HBO2(aq) .1H 0 = -28.8 + (-0.08) + 17.3 == -11.58 kJ
Ans: The standard enthalpy (.1H 0 ) of the given reaction is -11.58 kJ.
 __,.- - ~ - - - --========::;:=:::==::\ll~lb::J~=======::::::~=
' r 1 at 25 ° C .
,QJSZ· calculate Kp for the reaction, C 2H 4 (gl + Hl(gl--➔ c 1H6 (g), ~Go= -100 kl mo

50/lition: ~G 0 = - 100 kJ/mol = -100000 J/mo\, T = 25 °C = 298 K

o;ven: KP for the given reaction
nd
rofl : ~G 0 = -2.303RT log 10 Kp
formula: ~G 0 = -2.303RT log10 Kp
ca/cufation:
-100000 - -2.303 x 8.314 x 298 x log ,o Kp
100000 = 5705.85 log10 Kp
100000 = log10 K P
5705.85
Taking Antilog on both sides,
Antilog [17.5258] = Kp
3.356 X 10 17 = Kp
17
Kp = 3.356 X 10 1'7
,-
0 ,., ~ A "I v- \ rn n
for the given reaction is 3.356 x 10 ,. "r;no , ~ -
s: The K
 4

-- ~-UH. Kp for the reaction, Mgco3(s) --'J~Y

Solution: _ ua.uucauy
+ MgO(s)
• un:sLau
+ C02(g) isic;9. X 10 . Go for the reaction at 25 oC
-10 Calculate A ·
G iven:
To find: Kp = 9 x 10-IO, T = 25 °C = 298 K
L\GO
Formula: d.G 0 - -2.303RT log Kp .:J :o~to ::;;: _l O. 9.5 42
- , . f7ff·l ~ --1..9~0458
Calculation: d.G 0 - -2.303RT log 10 Kp \;-4 _. ·298 X 9.0458 - __
0 10
~~//:'\,,
- : :· 2 c:303 -__ _. + l0 g· g · 314 + log 298 + l_og 9.045&
~G -2.303 x 8.314x 298 x log 9 x 10-10 ;,_B
_-:_
·'.-' _:~:"' - + - - + 2 .4742 + 0.9565
-_ 0 ·9198
-

=== 51,613.72 J mo1- 1

:~6i3
0 7128) _
~G = 51.61 k.J mor1
0

Ans: ~G for the given reaction at 25 °C is 51.61 kJ mor1 •

~-~-------~------------------------- --
 --~== = = = ==========================::::::::::d'l!I~ ::::::=::::========:=:=:~~~~=-::::
~~1 ~ *Q.185.
•
Calculate AG for the reaction at 25 oc' CO (g) + lH 2(g) -~>~ CH3 OH (g), AG 0
1
= -24.8 kJ mol ;

if Pco = 4 atm, p" 2 = 2 atm, p CH 3 0H

= 2 atm
Solution:
Given: .1G 0 = -24.8 kJ/mol, T = 25 °C = 298 K, Pco = 4 attn, pH 2 = 2 atm, P cH3 oH = 2 atm
To find· .1G
Formula: .1G = .1G 0 + 2.303RT log 10 Qp
Calculation: .1G = .1G 0 + 2.303RT log 10QP
Q = P cH 3 oH _ 2 = 2 = 0 _125
P
P co x
(
PH 2
) 2 4x(2) 2 16

.1G = -24.8 + [2.303 x 8.314 x 10-3 x 298 x log(0.125)]

= -24.8+[-5.153]= -24.8-5.153
= -29.95 kJ mol- 1
Ans: The .1G for the given reaction at 25 °C is -29.95 kJ mol- 1.
 - --- -•~ u '-'.L H VU 1 ~ ~JJUIILitll it: UU ,3 y • ~-
*Q.156. C alcul t ""S • • · spontaneous at 25 °C.
a e a tora1 and hence show whether the following reaction IS
HgS + 0 J K-1
Solution: (s) 2(g) ► Hg(/) + S02(g), AHo = -238.6 kJ and ASo = + 36. 7
Given:
To find:
! = 25 °C = 298 K, ~H 0 = -238.6 kJ, ~S = + 36.7 J K- 1
0

1. ~Stota1 11. Spontaneity of reaction

Formulae: ~Ho
I. dSsurr = sys
11. ~Stotal ~Ssys + ~Ssurr
T
~H
Calculation: AS SUIT - = - (-238.6kJJ = 0.8006. kJ/K = 800.6 J/K
0
L..1 - .
T 298K
L1Ssys ~S 0 = + 36.7 J/K
L'.\Stotal ~Ssys + ~Ssurr = 36. 7 + 800.6 · 837 .3 J/K
Ans: ~StotaI = 837.3 J/K. As AStotal is positive, the reaction is spontaneous at 25 °C.
 Q 118. Determine whether the reactions with the following AH and AS values are spontaneous or non-
~ · spontaneous. St ate whether they are exothermic or endothermic.
i. AH= -110 kJ and AS= +40 J K-1 at 400 K
ii. AH= +50 kJ and AS= -130 J K-1 at 250 K
50/ution: .
Given: 1. ~H = -l l0 kJ and ~S = +40 J K- 1 at 400 K
ii. ~H = +50 kJ and ~S = -130 J K- 1 at 250 K
To fi nd: Whe th er th e reac~ions are exothermic or endothermic and spontaneous or non-spontaneous.
formula: ~G = LlH - T ~S ,
Calculation: i. Refer Q.177. i.
ii. LlG = LlH - T~S
LlH = + 50 kJ
LlS = -130 J K- 1 = -0.130 kJ K- 1
T = 250 K
~G 50 kJ - (250 K x -0.130 kJ K- 1)
= 50 + 32.5
= 82.5 kJ
As ~G is positive, the reaction is no·n -spontaneous.
As ~H is positive, the reaction is endothermic.
Ans: i. Reaction is spontaneous and exothermic.
ii. Reaction is non-spontaneous and endothermic.