Thermodynamics Theory H

"manishkumarphysics.
in"
1
CHEMISTRY
ainfa+t
sf4
ainfa+t (Thermodynamics) lai- +i t ziiii l=n -i + lli-- i -ii --+ ~-- l- -i +i ~-
l+i i-i t =i- lai- n :=+ ln( -ninl-+i < +- l+i i-i t
ainfa+t
"ekxfr d h
d k i zFke fu; e
"ek j l k; u
j kl k; fud v fHkf; kv ksaesa
i zFke fu; e d sv uqi z; ksx
"ekxfr d hd k
f} r h; fu; e
ainfa+t + ui4a faia as4in
l< <i <iii +i lnnii i( - --n ~lil+i ti ni i -ti t -i nnii i =+-i t (~lil+i + ti -
+i =i --i)
l< ~lil+i ti -i t -. ~lil+i + <i i- -i n +i l- - ti - t . t ai- ti -i t
l< i=il-+ ~lil+i n =i-i-ii -iil- ti -i t -. lli-- ~li+i+ -ii -i< +i =i- =i-< -i +i
ti ni. t -ninl-+i ,ii l+ln- l+i i =+-i t
ainfa+t +t uti4
-ninl-+i + l-n + n ~li+ nizii n <iii -ii =- i - zi nin ti - t t (+ lnln- (llzi i
l+-n-) +i~i nin -ti ti -i t -i. <i (-i -i. ~il<. =- i - zi + ln( ni-i i-i t
-ninl-+i + -i n = tn ~lil+i + i ti - n ~ii i=il-+ =i- +i i-- +- n nn =n +i ni-i
n -ti + =+- t
Ex. A + B C+ D K
1, eq
= 10
3
E + F G + H K
2, eq
= 10
3
l--- n = +i -=i ~lil+i =i-i-ii +i tn (-<i) i-- + ni `
Sol. t tn ai- -ti + =+- t +i l+ =i-l-ii + +i =i- i-- +- n nn =n + =ii +i: =--i -ti t
=i- l-ii + K +i ~li+ ni-. ~ii- =i- -i< +i =i-< -i ~li+ ti -i t
=i- l-ii+ K+i +n ni-. ~ii - =i- -i< +i =i-<-i +n ti-i t
ainfa+t as4int {s4a) s<
(a) ai (System) -i l- - + ~- + ln( lni ni ni +i iin
Ex. +n n i . i -n n i-i. -ii +i : =i --
sfzi (Surrounding) ni +i zi i -i t ~i iin
oi (Universe) : - zi + lzi = ni
"manishkumarphysics.in"
2
CHEMISTRY
sfuti (Boundary) t + z ii i - zi -ii l zi +i i+ +-i t l=ini +tni-i t
l=ini. i--l+ +i-l-+ <i -i ti =+-i t
l=ini. <c -ii n-ini <i-i ti =+-i t
-<i. + ln(. n-in n i n i . (n-ini l=ini) l+ +n n i (< c l=ini) l=ini zi n (~-in+i)
~ii -in+i(diathermic) ii ti =+-i t
(d) a i + s +i :
(1) iniai (Open system) - zi i <ii -ni <i -i +i l zi + =ii ~i<i- <i- + (-<i. =i - zi (+i :
=i iii). ini- zi +tni-i t -<i. (+ in +n n i
(2) < a-i (Closed system) : - zi i (l zi = ) + n -ii +i ~i<i- <i- +-i t <ii +i -ti < - zi
+tni-i t -<i. < izi n +i : ii <ii
(3) fnfna ai (Isolatedsystem) : - zi l=n -i -ii <ii l+=i +i ii l zi + =ii ~i<i- <i- -ti ti -i t
a<iri
(1) in = +ni-+ n n (t i - lnln- - zi -ti t -- := + z zi =n ~--in + ln( lnln- ni-i
i =+-i t +i l+ :=n -i +i -ii-i--i -n ti-i t
(2) =-i i (+ i -- lnln- - zi t
.
ini ai -< ai fnfna a i
(2) a i +t ii4 :
:=+i ~i t ll-il- l=n -zi t
:= - zi + + z nil- ~ii l-i- n ii = l+ <i. ~i--. -i. <ii +i nizii. i-i-i -niiil-i ~il< +
ni- ~ii llzii+i ,ii - zi liili- ~ii llzii+ - l+i i =+-i t
a<i (+ ~i<zi n = - zi + ln( - zi +i ~-ii. - zi + llzii+ - ~i--. -i -ii <i ,ii liili- l+i i =+-i t
~- - zii + ln( tn ~li+ n ii +i llzii+ - + =+- t i - zi +i = + n-i (ln-i) l-i +- t
ii +na (State functions) :
+i : n i i -zi +i + n ~-ii l-i +-i t ~ii - t (+ l-< +n- t
t (+ l-lz-- ~-ii +i i-- +- + i = -- zi ti-i t
a<i. (i lzi+i n l+=i -- +i l-ii- ~-ii +n- t +i -- ,ii - +i n: < i i +n- t
l+=i -ninl-+i -zi + ln(. -i. <i. ~i--. +n ~i--l+ -i (E -ii U), (-i-i (H), ln= n+- -i
(G), (- ii (S) =ii ~-ii +n- t
-i+- -<iti n <i-i ii n ~l--n -i. <i ~i-- =ni- t -- :=n l-lt- +i -ii +n + <i i- -ni
+i l--. li--li-- tini
3
CHEMISTRY
si +na (Path function) :
t n i i (+ l-lz-- ~-ii +i i-- +- + -i+ (lli) ~ii i l-i +- t . i +n- +tni- t
a<i. -ni. +i. -ni iil-i (nin -ni iil-i. llzi -ni. iil-i. ~il<).
t +n + <i i- ti liili- ti - t -ii -ni nl-+i - zi (+ ~-ii = =i--ii < =i ~-ii n ll- -
ti -i t t - zi +i l-lz-- ~-ii n (+ l-lz-- ni- -ti i- t
ni ri + s+i
iii-+ 4i fai-+ ni
- zi + +n- ~ii ni i l+ - zi + ~i+i <ni- l-i +- t --t niziin+ n i +t- t
niziin+ n i + l- n i nin+ ti - t +n + <i =ni- iini +i ~i--i +i i n +n + =- i ~i-- + i
ti -i t
a<i. ~i--, <ni-, +n -ni iil-i, +n ~i--l+ -i (-i-i(H). ln= n+- -i(G). (-ii(S)
iii ai ni (Intensivefunctions)
+n- i n i i +i < ni- ~ii ~i+i l-i -ti t- t nizii -- zi n i +tni- t
nizii -- zi n i +i + l- i nin+ -ti ti -i t
a<i. -i, <i, nin -ni iil-i, llzi -ni iil-i, i-, =i<-i, i <i
iii-+ aii iii a i n iri +t sria
l< l+=i l-lz-- ~-ii n (+ - zi + =ni- i ~=ni- iin l+ i- t - n i l-+i ni-. =- i - zi + i--l+ ni-
+ i i =ni- ti -i t -i --t nizii -- zi n i in +t- t l+ n i. l-+ ni-. =- i - zi + i--l+ ni- = l---
ti - t -i --t niziin+ n i +t- t
300 300K 300
1L
2L
1L
1atm
1atm
1atm
K K
d ej sd ksnksl eku Hkkxksa
esafoHkkft r fd ; k x; k gSA
a<i. 300K -i, 1 inni <i +n n i -l-i- t ~ l< +n +i =ini (~iii=i ~ii i--l+
lii- ii) ,ii <i iini (=ni- ~=ni-) n liil- l+i ni t
~ <i-i iini n -i. <i. i-. n= ~i ~i +i =i < -i + ni- ~il< - :- <i -i iini n =- i - zi +
-- zi nizii =ni- t n
l+ <i -i iini +i ~i-- n = ~i ~i l+ + n -i <i -i iini n n = +i ii <i -i iini l+ (- i i. ~il<
+i ni- i-i n =- i - zi + ln( :- n ii + ni-i = li-- ti n (<i -i iini + ~=ni- ~i-- +i i n +n
+ + n ~i-- + i ti -i t )
ainfa+t ui4 :
- zi n =n + =ii l+=i l-i- -ii nil- n i n +i : l- - -ti ti -i t - - zi +i -ninl-+i =i- n
+ti i-i t
-ninl-+i =i- -i- +i + =i- i-i t
(a) i lzi+ =i-
(b) -ii =i-
(c) i=il-+ =i-
4ifi+ ui4 (Mechanical equilibrium) :
- zi n (=n -ii -ii- + =ii) +i : <i i-i -ti ti -i -ilt (l+=i ~i<zi n = - zi + ln(. l+=i < - zi + ln(
ti -ii- + =ii <i i-i ti =+-i t izi ~ii - zi + < n ~li+ < + +ii < +i =-t +i - n-i n <i
i-i ~li+ ti -i t
4
CHEMISTRY
aist4 ui4 (Thermal equilibrium) : ti +i: -i i-i li---i -ti ti-i -ilt
T fu; r l eku =
- zi n -ii-l-il- + ~-=i -i li--li-- ti =+- t -- =n + =ii t l-- t-i t
iui4fa+ ui4 (Chemical equilibrium) : ti - zi n l+=i il- (species) +i. +i : ii =i < -i i-i -ti
ti-i -ilt
ii 4i sfifa + irii s ai nfa+t s+ + s+i
ainfa+t s+ (Thermodynamic process) : +i: ii lli +n l=+ ,ii -zi :=+i (+ -ninl-+i
=i-i-ii = <=i -ninl-+i =i-i-ii n i-i t
ti ~--- +i + -ninl-+i +n ti =+- t :-n = +z l--- ni t
1. uaist s+ (Isothermal process) : T = l--
dT = 0
AT = 0
2. u i4aat s+(Isochoric process) : V = l--
dV = 0
AV = 0
3. u<it s+(Isobaric process) : P = l--
dP = 0
AP = 0
4. =zi s+ (Adiabatic process): q = l-- lzi + =ii -ni +i ~i<i- <i- = 0 (zi-)
+n ti - + -i+i llii + ~iii -ninl-+i +ni +i l--- +i ni+- l+i i-i t
a-+it4 s+ (Reversible process) : (+ +n i +i t - +n l- - = -+nii +n +tni-i t
l< (+ +n := +i +ii i-i t -il+ - zi l+i + t -- -ninl-+i = =i- n t
l< +n := +i ti -i ti . l+ -in+ n ( l- n) -ii. l-n n ~ - = -n (-n) ~ - ti -i t
:= +i +n t - ti =-n i iini nl- = ti -i t
F
-in+
= F
ll-
dF -ii dF 0
(+ ~i<zi -+nii +n + i ti- + ln( ~--- =n nnni
t ~lil+i ~--- = iin ti -i t
- = +t =+- t l+ lzi n +i: ~i<zi -+nii l+i -ti t
(+ -+nii +n + l-i + ln( tn l--- -zi l-i +- t
(+ izi n . ~i<zi n = +i < ni- lt- l-- l= - +i i (pile of sand) n ii ti . -ii + - + +i
+i <ni- -n t
5
CHEMISTRY
-+nii =i +n + ln( tn iiii - + +ii +i (+ + i< (+ (-n <niin ) ti+ <ni- +n
+- t := +i n = +i =i ~ - = -n < = ii ii ti ni -ii tn zii - zi -ninl-+i =i- n t ni ~- =i
-+nii +i +i tini
l-- +i (n = - n- ~i i) +i l-zi (FBDof piston)
l-- + =i--ii n ~i- + ln( :
P
gas
= P
atm
+ Mg/A
a-+it4 s+ (Irreversible process) : l< +n := +i +ii i( l+ +n l=. ~- l-- ,ii
( +nii) -ti l+i i =+-i t . ~- +nii l- - +tni-i t -ninl-+i - zi + n il-i+ -ii ~l--n ~-ii
n =i-i-ii n ~i-i t -i l+ l+=i n-i ~-ii (~ii - zi + n + z l-lz-- = i +i n-i ~-ii~i n
ti. -ninl-+i =i- ~-ii n ~i-i t a<i. n < n n= +i ~-+nii =i n n < ~i- t
l< +n + <i i- ti + n -ii l-n + n (+ l-lz-- ~-- ti -i t := +i +n (+
l-lz-- < + =ii =--- ti-i t
''a-+it4 s+ y+ fafza u4 si rini''
~- +nii +n +i n-i ~-ii ~nn ~nn i +n- = <i. -i ~il< +i liili- -ti +
=+- t
=ii i--l+ +n ~-+nii ti- t
-i + - zi +i ~- +- . l< l-- + - (+ i i+ nni+ tii
i( -i l-- - ~--- i + =ii -+ nl- +-i t l= ~i -+
+i n = +i <i. ir
<i + =ni- -ti ti i-i t ~- +n (+ l-lz-- =n n i ti i-i t
P
xSl
nzO; eku j fgr
xfr eku fi LVu
P
ok; q
xSl
j ks/kd
-ii ti + n -ii l-n n (+ l-lz-- ~-- ti -i t := +i - zi + ~- +nii +n + <i i- n = + <i
+i liili- -ti l+i i =+-i +i l+ li--li-- -ii-i <i + li--li-- ni- i i- t
~-+nii +n l-lzl-- =n n i ti i- t :
-i -ii-i--i + +i
ai aii +i4 (Heat &work) : t <i -i+ t l== - zi. l zi + =ii ~-i - l+i (interact) ~ii -i +i
~i<i-<i- + =+-i t
-ni -ii +i. -i + t
ai (Heat) : - zi -ii l zi <i -i + n -i n ~-- + +ii -i +i -ii-i--i = ti -i t t -ni +tni-i
t
+i4 (Work) : -i -ii-i -i. i -i n ~-- + +ii -ti ti-i t ~i i -ni ii -ti t . +i +tni-i t
+i t - = +i + ti =+- t = i lzi+ +i . l - +i . - -+i +i . n i +i ~il<
-zi + -- ~- =i (l+- + ~-=i) -i -ii-i -i +i +i ~ii =ni- -i +i -ni +ti i =+-i t
:=+i =nn- + ln( -i- l<ii - zi +i ~- +- t l=n l+ 25C, -i (+ izi n n lni i-i t -ii
l zi +i -i ii 25Ct ti (+ -ni + ni t i n n i t -ii i = (+ + i ,ii (S) ,ii i t
i-i n -ni + ni ii 25C-i t ~ ti 2 -i+ t l-n - zi +i -- +- t ( -ni +i +i - -i
+-i t
25 C
0
25 C
0
S
e
"eh; d q. My h (25 C)
0
6
CHEMISTRY
Iai (ISystem) : izi + =ii = na+ (i+) (n -ii -ni + ni).
+ i i-i +i i-i t - - zi + -i n - -+ lz ti - nn-i t -+ +i l zi +i -i. - zi + -i + =ni-
-ti ti i-i t := +i ~ -ni it -ti ti -i t -- ~ii ii - zi +i -i n lz ti ti t -ii := +i - zi
+i -i ii c ti t t i + ,ii - zi l - +i l+ i- + +ii ti ti t . -i l+ -ni -ii-i -i + +ii.
l+ i-i n -i =ni- i
IIai (IISystem) : + n n tnii - zi t . -ni + ni. l zi +i iin t := ll-il- n + i -in
+i i-i t - -ni + ni +i -i tn c-i t := +i ti - zi l zi + n -i n ~-- ~i-i t
:= +i t -i -ii-i-i. -ni +tni-i t
f+4i n4i +i4 (WORK DONE) (w) :
-i +i (+ - zi = < = - zi n := +i -ii-i--i. l=n +i -i ~-- -i = l-lt- (=l-nln-) -ti ti . +i
+tni-i t t i +n- t -ii ~- tni =nn- + ln( +i +i dw = Fdx + n +- l+i i =+-i t ti
n F l -. --+. n ~il< ~- -zii -i ,ii --- l+i i =+-i t
r+ir :
+i -ii -ni <i-i ti -i + t := +i :-+i :+i:i ii -i +i :+i: t
SI ai : n (J). ~li+i zi ni- (data) i-i :+i: -zi + ni i n -ni t
~- := ii +ii+ii -i n n nii i-i t
fasit : (niinn) i -i +i :+i: +i +- +- t.
:-+ ~-- l-- +i <iti- -ini tini
(1 ni. inn = 101.3 n = 24.206 +nii)
~- +nii +n + ln( ~-ii < = l+ P, T ~il< +i liili- -ti l+i i =+-i t := +i P n = + -i n
,ii +i +i l+ln- -ti l+i i =+-i t -- +i. -i n + ~- =i (+ ,ii) l+ i =+-i t
W
gas
= W
ext
+ AK
pisston
l-- lini-ii n <i ii ~i-i t AK
piston
= 0
W
gas
= W
ext
=
dv P
ext
}
:= +i in<i +i tn zii liili- + =+- t -ii + +n + ln +i +i ni-i
W
ext
=
dv . P
ext
}
+i4 : dW = F
ext
dx
P-V +i4 :
ni-i +i inn F
x
t -i l-- dx <i + = -i- +i -+ nl- +ni
F
ext
dx
) dx A (
A
F
dW
ext
= dW = P
ext
(dV)
-i +- ll-il- n ir +i+ ,ii l+i ni +i +ve -ii := + + n +- +- t . ~-ii -ve l--t nnii
i-i t
dW = P
ext
. dV
7
CHEMISTRY
+i4 aii ai + fny IUPAC f-r sfaa
--zi +i <i n: l+=i ii +i +i -i +i i-in+ ni-i i-i t :=ln(
--zi +i <i n: -ni = i-in+
--zi + ,ii it l-+ini n: -ni = +iin+
--zi l+i ni +i = i-in+
--zi ,ii l+i ni +i = +iin+
l--t l-- iil-+ lai- =i- lai- = ~nn t -- :=+i ~i =ni- l-+n+ ~i-i t =ni+ii n tn +i
+ ln( ~nn~nn l--t i--i +i -in + =+- t
l< =n-i n w= 10 J t -i :=+i n-n --zi ,ii lzi l+i ni +i 10 J t
ui4fa+ faia + aui
Aw
AQ
Aw
AQ

In Physics
AU = AQ + AW AU = AQ AW
--zi l+i ni +i =+ve
-ni +i IUPACl--t l--
1. --zi +i <i n: -ni = +ve
2. --zi + ,ii it l-+ini n: -ni = ve
3. --zi l+ ni +i = +ve
4. - zi ,ii l+i ni +i = ve
i<zi nu s ffi-a v+i +t vf+4i + fny +i4 +t niai
(A) uaist4 vui ti +: v+i = n= +i =n-ii = v=il- + =+- t
(i) y+n s<t4 uaist4 vui
<i n: =ni+i n tn v=i +i i nni <i + lz ni-- t ni-i +n vil-i+ =i-i-ii +i -i i-
+ ln( vi-i n l-- m
0
< ni- +i ii ii i-i t
P
i
= P
gas
= P
atm
+ m
0
g/A
PV diagram Representation
v=i + ln( m
0
<ni- + ii +i ~-i-+ ti l<i i-i t -i l-- ir <i P atm+ lz n = =il- ti-i
t := l-il- n n = + <i +i liili- -ti + =+- t . +i l+ ~-i-+ v=i = . -n - + =ii ~i (+ =ii v=i
-ti + i- t . :=ln ti =n ~--in ~i i-i t . := l-- +i l-il- (state of turbulence) +t- t
8
CHEMISTRY
~i-- v +i l+=i n-i ~-ii = n = + =i n + z +i l+i i-i t
V (V + dv)
dw = P
ext
. dv (IUPAC l--t i--i)
so W = } }
=
f
i
V
V
ext
dv . P dw
W = P
ext
(V
f
V
i
)
:=ln(
+ n vil-i+ -ii ~l--n ~-ii +i -i- t (n-i ~-ii n n = + <i +i liili- -ti +- t )
fzs<t4uaist4 vui
< ni- M
0
+i <i iii n liil- l+i i-i t (<i -i ii =ni- i ~=ni- ti =+- t )
) m m ( M
2 1 0
+ =
~ l< m
1
+i +n tii i -i l-- i <i + lz n= +i v=i l<ii: <-i t
P
ext
= (P
atm
+ m
2
g/A)
-ii t v=i + n ~i-- v
1
-+ ti-i t
P
ext
. V
1
= P
i
V
i
(isothermal) =n-ii
~ l< l,-i ii M
2
+i tii i -i
Vi V
f
l-- <i + lz vi-- tini
P
ext
= P
atm
~-
Vi V
f
-+ v=i n l+i ni +i
W
1
= (P
atm
+M
2
g/A) (V
i
V
1
)
-ii :=ln V
1
V
f
-+ v=il- +i
W
2
= P
atm
(V
f
V
i
)
+n +i = W
1
+ W
2
P
atm
V
V
f
M
0
V
i
M
1
PV Diagram representation
< ni- m
1
-ii m
2
+i-l-+ t . :=+i i-- n ~iz+-i -ti t t v=i +i <i <i n -i- + ln( -i n
l+ n t
~-+nii v=i n l,<i v=i n n = ,ii l+i ni +i (+<i v=i = ~li+ ti-i t := v+i lzi<i
v=i n m
0
<ni- +i m
1
, m
2
-ii m
3
n liil- +- t -ii (+ (+ :-t tii i-i t
9
CHEMISTRY
n <i v=i + ln( n
ni-i l+ vil-i+ <i P
i
-ii =i-i-ii -i i- + ln( m
0
< ni- +i vil-i+ - i- t . :=ln(
p
i
= p
atm
+
|
.
|
\
|
A
g m
0
A = l-- +i ~- v-i +i -izi+n
~ l< - + c = +z nizii n - tii i-i t - -i in <i tini
P
ext
= P
atm
+
A
) dm An (
g
i <= zi< n
P
ext
= P
g
dp
= l-i-- = +t =+- t l+ vl+i := v+i = +i: i-i t -il+ --zi tn zii =i-i-ii n t ni -ii vl+i + l+=i
ii --
P
ext
= P
gas
dp
W
ext
= }
2
1
v
v
ext
dv . P
= }

2
1
v
v
gas
dv ) dp P (
=
) dv P (
2
1
v
v
gas
}
= }
2
1
v
v
dv
V
nRT
= nRT in
2
1
v
v
W = nRT ln (V
f
/V
i
)
:= v+i PV ni+ n := vl+i +i v<lzi- l+i ni t
10
CHEMISTRY
t tn ni- =+- t l+ p
f
= P
atm
ti-i t
:= =n-i n < - +i ~iz+-i -ti ti -i t n = + <i +i n-i ~-ii n liili- +- t -ii := v+i PV
n i+ n vl+i +i -ii ni t
(B) i<zi nu +i uaist4 usta :
vi s< usta
n= +i =-il- +- + ln( <ni-lt- l-- ~-i-+ m
0
<ni- +i ii i- t
dw = P
ext
. dv
= (P
atm
+ m
0
g/A) dv
:=ln( n= l+ n + n +i +i ni-i
W =
} }
=
f
i
V
V
dv . Pext dw
W = P
ext
(V
f
V
i
)
fzs<t4 usta
m
0
< ni- + ii +i <i iin (m
1
+ m
2
) + n ii i-i t n i+i v<zi - ,ii l+ n +i +i ni-i - t
l< m
1
+i tn i+. i <i + lz vin =-i- n l+i ni +i
(P
atm
+ m
1
g/A)
:=ln( W
1
= (P
atm
+ m
1
g/A) (V
1
V
i
)
W
2
= (P
atm
+ m
0
g/A) (V
f
V
i
)
t -+nii =-i- +i -t ti-i t
~i<zi n= +i =n-ii -+nii =-i-
- + +ii +i (+ + i< (+ ii ii i+ l-- -i n = +i =-i- vi-- +- t := ll-il- n l+i
ni +i -+nii vl+i + ,ii n = n l+ n +i + =ni- vi-- ti-i t
W = nRT ln(V
f
/V
i
)
t -- = i-in+ l-+n + ~i-i t :=ln( V
f
< V
i
t
11
CHEMISTRY
P
atm
V
i
V
i
(P + M g/A) = P
atm 0 f
V
i V
f
P
atm
fa+i ii n = +i l+i i-i t - -+nii vl+i n l+i ni +i - --n vi-- ti -i t :=ln( ~nn
nzii-:-- +i -+nii +i + ~-=i l-nii l+i i-i t :=ln( :=n ~li+-n liin vi-- ti-i t --
---n :- l<i i-i t
l-n- (out put) : :--nzii---zi ,ii l+i ni +i
~in- (in put): l zi n --zi ,ii l+i ni +i
l< v=i=-i- l-- i <i + lz l+i i-i t -i t ~-+nii ti-i t
l< ~-i-+ l-- ti-i t -i vl+i ~-+nii ti-i t
-+nii -ii ~-+nii =n-ii vl+i
~--- =-i-v=i + ~nii. =ii vl+i ~-+nii t
tn - -+nii -ii ~-+nii +i := v+i = ii v<lzi- + =+- t
-+nii vl+i l< (+ +n := +i +ii i -i :=+i il-i+ l-il-
= +i -ii -ni + n --zi -ii l zi + =ii i= ~-i - ~-ii n ~i-i
t -i := -+nii +n +t- t B
A
vl+i AB + ln( . +i = w . -ni = Q - l< vl+i + ln( BA . +i = w. -ni = Q - vl+i
-+nii t
l< =n-ii vl+i n i <i l-- t -i +n ~-+nii ti-i t
Ex. 25C -i 2 nin ti: i - +i 15 = 50 ni -+ =n-ii -+nii = =il- +- l+ n +i +i
ni-i l+l
Sol. tni i= t
W = 2.303 n RT log
1
2
V
V
= 2.303 2 2 298 log
15
50
= 1436 +nii
Ex. l< (+ n= 10 inn -ii 300 k -i t :=+i 2 inni l-- it<i ~i-- 10 ni = 20 ni
-+ =il- l+i i-i t -i l+i ni +i ai- l+l [=n-ii +n]
Sol. ~-+nii +n
] 10 20 [ dv 2 w
20
10
= =
}
= 20 J.
1 ni inn = 101.3 J
12
CHEMISTRY
i<zi nu +t ainfa+t4 sfiiii
l< n= + ln( ~i--l+ -i. :=+ n -i + =ii =ni-i-i ti-i t . - n= + := < +i (+ ~i<zi n=
+t- t
:=ln(
T
V
E
|
.
|
\
|
c
c
= 0 ,
T
P
E
|
.
|
\
|
c
c
= 0
~i--l+ -i (E, U = ii -ii i-i t ) :
<ii +i + nizii = =- li- t --zi +i (+ l-lz-- -i +i nizii +i ~i--l+ -i +t- t
--zi n -l-i- =ii -i ~i + +i i n := +i t
E = E
Translational
+ E
Rotational
+ E
Vibrational
+ E
bonding
+ .....
AE = E
Final
E
Initial
.
AE = q
v
, l-- ~i-- n= +i <i n: -i. - l+ n= +i <i n: -ni + ,ii ~i--l+ -i n lz ti -i t
t (+ niziin+ niin -ii (+ ~-ii +n- t t -i +i +n- t l< AT = 0 -i AE = 0 t
a-iai +t +ifa (+ ~i<zi n= + ~i + ,ii ++ + <ii- -i + l-- +i -i- + +i
+ +n iin +i :=+i ---zi-i +i +il +t- t
---zi-i +i i--l- +i l =3 =ii v+i + n =i + ln(
---zi-i +i i i - +i l
= 0 (+nnii n=
= 2 l,nii i ii n= tnii
= 3 ~ii tnii n=.
l< ' f ' n = + ln( vil-i+ ---zi-i +i +i l t
f = 3 (+nnii n=
= 5 l,nii i ii tnii
= 6 ~ii tnii
ai + uia sia +i fa4
~i<zi n = vl- ~i + =ii v + +i ---zi-i +i +i l = =-l-i- -i
2
1
KT + i ti -i t
U/~i = f x
2
1
KT
U/nin =
2
f
x KT
U/nin =
2
1
RT
n ni n + ln( =
2
f
nRT
U=
2
f
nRT +n ~i<zi n = + ln(
ai +t niai (q):
-ni (+ i +n- t -ii := =ini--i -ninl-+i +i in l-n + ,ii ~v-i = nil- + =+- t
l< tn l+=i vl+i +i llzi -ni < ii t -i tn AE -ii W +i ni-i +- t -ii :=+ i< q i
-ni +i ni-i +- t
-ni iil-i (+ i +n- t -ii -ni -in-i( +i ~nn~nn v+i liili- t
i< ii l+ (+ <ii +i -ni iil-i l-- -ti ti -i t . t vl+i + v+i l-i +-i t . l= <ii nin
l+i i =+
13
CHEMISTRY
+n ai riifai
l< n v+n + ~--n - --zi +i -i 1
0
C = ci- + ln( ~iz+ -ni +i nizii +i . + n -ni iil-i +t- t
nli-i = C
T
=
dT
dq
T
q
=
A
A
= J/C
t niziin+ ni -ii i +n- t
:=ln( dq = cdT
=ni+n- +- q =
}
cdT
nin -ni iil-i
(+ <ii +i 1 ni n +i -i 1
0
C = ci- ~iz+ -ni +i ni n -ni iil-i +t- t
nli-i =
:=ln( dq = ncdT
q =
T nc ncdT A =
}
=ini-- C
P
-ii C
V
~i<zi n = + ln( -i n n ni i- t
ffzia ai riifai (s) :
(+ <ii + :+i: < ni- (=ni-- 1 g) +i -i 1
0
= ci- + ln( ~iz+ -ni. llzi -ni iil-i +tni-i
t
S =
mdT
dq
T m
q
=
A
A
= Jgm
1
K
1
:=ln( dq = msdT
q =
T ms dT ms dq A = =
} }
l-- <i -ii l-- ~i-- llzi -ni iil-i +nzi s
p
-ii s
v
= liili- + =+- t
C
T
= nC = ms & C = Ms
v+n n -l-i- (+ <ii +i +n -ni iil-i. ni n -ni iil-i -ii llzi -ni iil-i n =--i := v+i t
m = <ii +i M= <ii +i nin <ni-. n = <ii + nin +i =i
=n-ii v+n + ln( C = =n<ii v+n C = C
p
=n~i--i v+n C = C
v
zin v+n C = 0
-ni iil-i +i ni- v+n + ~-=i = -+ ti =+-i t
Ex. ~i<zi n = + v=i + <i i- n = + ,ii l+i ni +i 100 s t -ii v+n +i -ni iil-i 2J/
0
C t l< n = +i
~l--n -i 25
0
C t i vil-i+ -i = ~li+ t -i n = +i ~l--n AE t
Sol. := v+i tn < i- t l+ -niiil-i (C) (+ i +n- t -- C
p
-ii C
v
i +n- -ti t :=ln( t l-- t
ainfa+t4 +i vi fa4
-i =-ii +i l-n
i +i + n -i tn zii = l-i- t-i t
i
(+ lnln- --zi +i + n -i tn zii = l-i- t-i t
i
:= v+i E + n ni- +i ni-i -ti +i i =+-i t + n v+n + ln( E + ni- n l- - +i ti ni-i +
=+- t
14
CHEMISTRY
-ninl-+i + vin l-n +i nli-i
l< (+ --zi l-lz-- ~-ii n vi-i n + n ~i--l+ -i E
1
i-i t l< := q nizii n -ni <i i -ii :=+
,ii w +i l+i i-i t -il+ - ~-ii n :=+i + n ~i--l+ -i E
2
ti i-i t - -ninl-+i + vin l-n
+ ~-=i
E
2
= E
1
+ q + w
so AE = (E
2
E
1
) = q + w
vin l-n +i -in
AU = AQ + AW -l+ AW = P AV
AU = AQ PAV
(a) l-- ~i-- v+n (=n~i--i)
du = dq + dw
du = dq pdv
du = (dq)
v
l-- ~i-- <i n: -ni = ~i--l+ -i n l--
du = (dq)
du =(nCdT)
v
du =nC
v
dT
l-- ~i-- llzi ni n -ni iil-i C
v
t
C
v
=
dT
du
.
n
1
=
dT
2 / ) fnRT ( d
n
1
=
2
f
R
(b) l-- <i v+n (=n<ii)
du = dQ + dW
du = dQ . PdV
dQ = du PdV ............... (i)
(+ - -ninl-+i +n- +i -in +n
H (-i-i
t (+ ~-ii +n- t -ii niziin+ ni t
:= nli-i = liili- l+i ni t
H = u + Pv
as dH = du + d (Pv)
as P = l--
dH = du + Pdv .............. (ii)
=ni+i = (i) & (ii)
dH = (dq)
p
+n l-- <i
l-- <i <i n: -ni = (-i-i n l--
dH= (nCdT)
p
dH = nC
p
dT
i<zi nu + fny C
p
aii C
v
uri
H = u + PV
dH = du + d(PV)
~i<zi n = + ln(
PV = nRT
d(PV) = d(nRT) = nRdT
nC
p
dT = nC
v
dT + nRdT
C
p
C
v
= R. + n ~i<zi n = + ln( = n =--i
AH,AU +i4, ai +t niai
sffifa I ~i<zi n= + ln( (+ v+n + ~--n -
-in n lni ni = zi
15
CHEMISTRY
du = nC
v
dT =
2
f
nRdT
dH = nC
p
dT =
|
.
|
\
|
+1
2
f
nRdT
W =
}
dv . Pext
dH = dU + d (Pv)
AH = AU + nR AT
dU = dQ + dw
Ex. 10 n in ti: i - l-- -i 273 K <i 20 = 1 i nni +- l+ n ~li+-n +i +i ni-i l+l
n= ~i<zi ti <zii -i t +i ti +i : ~i -l+ -i l- - tini ` q +i ii ni-i l+l
Sol. tni i= t
W = 2.303 nRT log
2
1
P
P
n = ti:i- + nini +i =i =
v.kqHkkj
Hkkj xzke es
=
2
10
= 5 nin.
:=i +i W = 2.303 5 2 273 log
1
20
= 8180 +nii.
~in -zi +i ~-ii n = = n= + ~- =i <n-i t-i t ~- l-lz-- -i ~i -l+ -i n l- - -ti ti -i t
AE = 0.
-, q = AE W = 0 ( 8180 ) = 8180 +nii
sffifa II ai = -ii < --zi + ln(
du = nC
v
dT =
2
f
nRdT (t ~i<zi n = + ln( -ti t )
dH = nC
p
dT =
|
.
|
\
|
+1
2
f
nRT (t ~i<zi n = + ln( -ti t )
W =
}
dv P
. ext
AH = AU + (P
2
V
2
P
1
V
1
)
dU = dq + dw
Ex. (+ < +i ~i-- 100 L -ii i <i 10 atm t t (+ zi n izi n -l-i- t < +i i <i ~-i-+
100atm -+ c i-i t . -ii :=+ <i + lz < +i 1 L = =-i- ti -i t -i -i~i
(i) +i (ii) AU (iii) AH
Sol. Work don = 100 1 = 100 lit atm
Aq = 0 Aw = Au
100 = Au
AH = AU + (P
1
V
2
P
1
V
1
)
= 100 + (100 99 100 10)
= 100 + 100 89
= 9000 lit atm.
1 lit atm = 101.3 Jule.
sffifa III i=il-+ ~lil+i + ln(
aA (s) + bB() + cC(g) aA(s) + bB () + c C (g)
W =
}
dv P
. ext
=
( )
}

i f . ext
v v P
= P
ext.
[(V
A
(s) + (V
B
() + (V
C
(g)
(V
A
(s) + (V
B
() + (V
C
(g)]
16
CHEMISTRY
= W = P
ext.
[V
C
(g) V
C
(g)]
= P
ext.
(
ext
c
ext
' c
P
RT n
P
RT n
=
. ext
c ' c . ext
P
RT ) n n ( P
W = (n
c
n
c
)RT
W = An
g
RT
dU = dq + dw
l< (+ l-- <i
dq = dH
dU = dH pdv
dU = dH An
g
RT
dH = dU + An
g
RT
Ex. 25C, -i . 1 nin < -i- + <t- + ln( l-lz-- <i ~lil+i +i -ni l--- +i <i i-i t
C
6
H
6
() + 7
2
1
O
2
(g) 6CO
2
(g) + 3H
2
O (); AH = 780980 +nii
l-i ~i-- ~lil+i +i -ni +i ti ni
Sol. tni i= t,
AH = AE + An
g
RT
ti An
g
= 6 7.5 = 1.5.
:=i +i, AE = AH + An
g
RT = 780980 (1.5 ) 2 298 = 780090 +nii
sffifa IV ~-ii l- - + <i i-
~-ii l-- =ini--i l-- <i -ii l-- -i +i: i-i t
:=ln( AT = 0
-- ~ii AH -ii AE ~zi - t (~i<zi n = ~nn v+n = )
+i l+ ~-ii l- - + <i i- <ii + ~i +i nl- -i =ni- t-i t -- l-il- -i ll- - ti i-i t
-ii E ti =ii v+i +i -i +i in t :=ln( AE = 0 t. :=ln( ~-ii l-- + <ii- A(PV) = 0 t
:=ln( AH = 0.
q = AH
~ -ni +i ni-i +- t =ini-- =+ni +i n -- -ni <i n: t -ii l-- <i t v+n +ii i-i t
q = AH
w +i ni-i + ln(
-i n
-ii -ninl-+i +i vin l-n +i -in ++ AE +i ni-i +i i-i t
Ex. l< CaCO
3
+i 100 g :=+ ~i -i: (aragonite) n ll-- ti -i t - q, w, AE -ii AH +i ni-i +i
l<i ni t l+ +-=i: +i i- 2 g/cc -ii ~ i -i: +i i- 2.5 g/cc t
CaCO
3
CaCO
3
+ -=i: ~ i -i: AH = 2 kJ/mole
=ini-- ai = ai = . ai = < . ai = <
= +ni W << q so. AE

~
q = AH
n=i i--i + ln(
-<iti ai= n = . < n =
q = AH
=
AE :=ln( W ti lzi i nt i-i t
17
CHEMISTRY
=&i v+
i = ~-in+i izi dQ= 0 (--zi -ii l zi + i- -ni +i l- - -ti ti -i t )
du = dQ + dW
nC
V
d
T
= PdV
} }
= dv .
V
nRT
d nc
T V
}
2
1
T
T
v
T
dT . C
= }
2
1
V
V
dT .
V
R
C
v
ln
1
2
T
T
= P ln
1
2
V
V
ln
1
2
T
T
= ln
v
c / R
1
2
V
V

|
|
.
|
\
|
1
2
1
1
2
V
V
T
T

|
|
.
|
\
|
=
|
|
.
|
\
|
T
2
V
2
1
= T
1
V
1
1
i TV
Y 1
= l--. pV
Y
= l--
t + n -ii ti ni- t PV
i TV
1
+i < + n -i l-+ (quasi) ~-ii i -+nii v+n +
ln( l-- t
~-+nii zin v+n + ln( t =ni+i ni- -ti t
=&i v+ +t vf+4i
(a) -+nii zin
vl+i + ~- =i zi n -ii =n-ii v+n =ni- t :=ln( =ii ll-il-i n =n-ii ~- +nii vl+i
+i zin vl+i -in + =+- t
l-- <i -ii l-- ni n +i =i =n-ii v+n +i ~i--. zin v+n = ~li+ ti-i t
V T
w =
}
dv P
. ext
, but P
ext
= P
int
=
Y
V
K
w =
}
dv .
V
K
, W = K | | ( )
+ +
1 / V V
1
1
1
2
=
1
V . V P V . V P
1
1 1 1
1
2 2 2

l+i ni +i =
1
V P V P
1 1 2 2

(as K = P
2
V
2
= P
1
V
1
)
18
CHEMISTRY
(b) a-+it4 =&i
=&i a-+it4 vui
W =
dv P
. ext
}
= P
ext
(V
2
V
1
) , or
} }
= dw du
w = Au
w= nC
v
(T
2
T
1
) =
1
) T T ( nR
1 2

=
1
) V P V P
1 1 2 2

l< <i ~-ii +i =--i zin -+nii -ii ~- +nii i + ~-=i l<i ni t
w
rev.
= Au
rev.
-- (+ u ~-ii +n- t
Au
rev.
= Au
irrev.
w
irrev.
= w
rev.
:=ln( +i (+ i +n- t
l< tn ( =i ni- l+
w
irrev.
= w
rev.
t -i-i t l+
Au
rev.
= Au
irrev..
~- U (+ ~-ii +n- t
<i-i -+nii -ii ~- +nii zi n i + ln( ~-ii A -ii B -ti t
< = zi (W
gas
)
irrev
, Au
rev.
> Au
irrev.
(T
2
)
rev.
< (T
2
)
irrev
-+nii v=i +i ll-il- n -i + ,ii n = +i ~i--l+ -i n +ni ~li+ nizii n ti -i t
P
irr
> P
reve
at V
2
19
CHEMISTRY
l< (+n < n (P
1
P
2
) +i <i cin ii-i ni t . l=n l-< 2' l-- lin ~-ii n vi-- ti -i t l<
l-- V
2
~i-- + i-i t -i 2'' l-< + ,ii (+n vin < n n = ,ii l+i ni +i
:=ln( (+n < n D< T
f
t . +i l+ l,-i < n ~i--l+ -i n +ni > vin < n ~i--l+ -i n +ni
:=ln( (l zi ,ii l+i ni +i) -+nii
(T
2
)
irrev.
>(T
1
)
rev
~- +nii i n ~i--l+ -i ~li+ nizii n c-i t :=ln( -i ii c ni
l< (+n < n =ni- <i + cin + +ii t l-< 2' l-- lin ~-ii n ~i i-i t
l< l-- (+n + < + ,ii lni ni i . - ~i-- v
1
= v
2
-+ =-il- ti -i t - l-< 2'' -+ t -ni
=&it4 a-+it4 vf+4i {ii +i+i +t niai)
~-ii A
vuqRe.kh;
~-ii B
P
1
,V
1
,T
1
P
2
,V
2
,T
2
W =
1
V P V P
1
) T T ( nR
1 1 2 2 1 2

=

= P
ext.
(V
2
V
1
) ,
1
1 1
T
V P
=
2
2 2
T
V P
n+- v=i tnzii ~-+nii = ti-i t -ii P
ext
= 0 t
~-
due = P
ext
. dV
= 0
l< -ni +i vit -ti ti-i t q = 0
- AE = 0 ~- AT = 0.
20
CHEMISTRY
s<ii +t y-ist (ENTHALPYOFASUBSTANCE) :
+ <ii . l-lz-- ~-ii n (-i -i +i l-- ni- i-i t l :=+i lzi z (l-lz--) niai- -ti + =+-
t nl+- t (+ l-lz-- ii i-i t
(+ ni n <ii +i (-i -i ni n (-i -i +tni-i t l+=i l-lz-- (l+n-) ~-ii + ln( l--t l< i =+- t
H
m
(<ii ). -<iti + ln( i nni. <i. 398 K-i n +i ni n (-i -i l--- +i <zii i i =+-i t H
m
(H
2
O, g, 398 K, 1 atm) t =n zi<i n <ii +i (-i -i +i -ni l- -i+ + n lni i-i t -ii ~lil+i
+ <i i-. t -ni --- ti =+-i ~ii ~zii li- ti =+-i t
~i<zi (ni-+) ll-il-i <ii +i ni n -ni iil-i ni-+ ni n -ni iil-i +tni-i t l+=i <ii + ln( ~i<zi
ll-il-i +i ~i t
ai ui4a (THERMOCHEMISTRY)
t il-i+ = i=il-+ - zi -ii :=+ l zi + n i=il-+ ~lil+i n -ni + -ii-i -i (+i ~- l+i
i-i t ) = =-l-i- t
i nziini n . ~li+i zi ~lil+i l-- i nni <i ti -i t := +i -ni +i -ii-i -i - zi +i (-i -i l- -
+ i ti -i t
l+ l< ~lil+i l-- ~i-- +ii i( - -ni l- -. - zi +i ~i -l+ -i l- - + i ti -i t
n = + ln( ni-+ l-il- l< n -i . (+ i ~i lzi+ <i ~i<zi n = t
< + ln( (+ i <i. -ii l< n -i (+ zi z < t
ziz l+-ni ai= + ln( l+=i l< n -i (+ i <i . zi z l+-ni ai = t
l+=i <ii -ii ln- n ~i- + ln( l+=i l< n -i . (+ i <i . -izii ( i-i) +i ni nn-i
:+i: ti-i -ilt (1M=i< -i ii ni i =+-i t),
n i +i 398 K ni n ni-+ (-i -i +i . H(H
2
O, g , 398 K) + n <lzi - l+i i-i t -ii < n +i
398 K -i nin ni-+ (-i-i +i. H
m
(H
2
O, l, 398 K) + n <ziii i-i t
tn <ii +i i--l+ (-i -i +i ni-i -ti + =+- t . -- (+ ~-ii = < =i ~-ii n (-i -i l- - +i ni-i
+ =+- t
For example :
ni-i +i l< il-i+ (-i -i
0
1 , m
H -ii ~l--n (-i -i
0
2 , m
H t
- AH =
0
2 , m
H
0
1 , m
H
l-- <i 25C= 50C-i l-- n ii n: -ni .
= C
P
AT = (18 cal/mole C) (25C) = 450 cal
Ex. i=il-+ ~lil+i + H
~li+i+
~lil+i -nizii ii ti -i -ilt ~- tn ~li+i+i +i ~l-l+- -ni < -i -i t l== t -i< n ll- - ti - t
-ii l< H
-i<
< H
l+i+i+
~lil+i -ni-i i ti -i -ilt ~li+i+i +i ~l-l+- -ni. ~lil+i + <i i- l-+n i-i t
~lil+i n (-i -i l- -: AH
~lil+i
= H
-i<
H
~li+i+
AH
~lil+i
= H
-i<
H
~li+i+
= i-in+ -ni-ii
= +iin+ -ni-ii
21
CHEMISTRY
uia +t y-ist {uia +t ai) (ENTHALPY OF FORMATION) :
<ii +i ni n (-i -i +i ni- =ti=ti (lzi z) ni- l-+in-i = i -ti t zl t l--- li ~iiil- t
lli-- <iii +i = i- ni-+ ni n (-i -i +i =i -i ni- -ii i =+-i t
+ - +i ni-+ = i- (-i -i. :=+ = n i- +i -iii ~-ii -ii (+ i nni <i -ii (+ llzi -i
zi- (ni-) ni-i i-i t t llzi -i =ini-- 25 Clni i-i t
+z -<iti t AH
f
(O
2
, g) = 0
AH
f
(C, n+i:) = 0 AH
f
(C, tii) = 0
AH
f
(Br
2
, <) = 0
AH
f
(S, il-+) = 0 AH
f
(S, ni-il+nl-+) = 0
AH
f
(P, =+<) = 0 AH
f
(P, +ini) = 0
<ii i iln+ +i ni-+ = i- -ni. ni-+ -ni n l- - (+ nin i ln+. ~- il-i+ -i +i ~iz+
nizii = :=+i -iii = n ii- ~-ii n --i t + z i=il-+ ~lil+i i i ln+ <iii + l-ni i +i = i- -ni
=-l-i- t = -i- <i ni t
HBr(g) +i = i- -ni :
2
1
H
2
(g) +
2
1
Br
2
(l) HBr(g)
AH
f
(HBr, g) = E v
B
0
m
H (B) =
0
m
H (HBr, g)
2
1
0
m
H (H
2
, g)
2
1
0
m
H (Br
2
, 1) ...(1)
SO
2
(g) +i = i- -ni : S (il-+) + O
2
(g) SO
2
(g)
AH
f
(SO
2
, g) =
0
m
H (SO
2
, g)
0
m
H (S, il-+)
0
m
H (O
2
, g) ...(2)
-- -i + ~lil+i . ~lil+i -ni l-+in- (ni-i +- ) + ln( -ti t +i l+ lli-- <iii +i ni n (-i -i
=ti=ti ai- -ti t
uia +t ai u fif+4i +t y-ist aia +ai
~lil+i (-i -i. +i ni-i +i i =+-i t
AH
r
= E v
B
AH
f
-i<
E v
B
AH
f
~li+i+
v
B
~lil+i = =ni+i lnl- nii + t
l+=i ~lil+i + ln( -i +- =ni+i =ti t =ni- = <i n ~li+i+ -ii -i< +i ~-ii + ln( -i ni t
(l-zi n <zii ~- =i).
2H (g) I
fud ky hxb "ek Z
H = 52.5 kJ mol D
r
1
H (g) + (g)
2 2
I
H
vfHkf; k dh, YFkSYi h
ekud v oLFkk esar Ro
v fHkd kj d
mRi kn
DH
r
0
Ex. ~lil+i ZnO(s) + CO(g)

Zn(s) + CO
2
(g). +i ni-+
(-i ni +i ni-i +i
l<i t l+
AH
f
(ZnO, s) = 350 KJ / mole
1
AH
f
(CO
2
, g) = 390 KJ / mole
AH
f
(CO, g) = 110 KJ / mole
22
CHEMISTRY
fa4a ai + 4in +i ru +i fa4
l< n: i=il-+ ~lil+i n -=l - i ~zii li- -ni =ni- ti -i t l< +n (+ -i n i ~li+ -i n +ii
i
i=il-+ =ni+i (+ =ini- lnli- + +i -t ti +-i t . -ii ~iz+ =ni+ii +i i + i ii
+ i-- + =+- t :=i +n n l< n: ~lil+i +i (-i -i ii ll- - ti -i t := +i ~iz+ ~lil+i + ln(
~lil+i +i (-i -i l< i-i t
A
r
H (-i-i + l-- +i -i-i t =ni- -i -ii <i l+i+i+ (-i = <ii -+ -l-i- <ii ). -i<
(-i = ii -+ -l-i- <ii ). n ll- - ti - t l< ~lil+i -+nii t (-i< +i ii -+ -ii l+i+i+
+i <ii -+ lni- t ) - ~lil+i + ln A
r
H=ni- t ni -- :=+i l--t ll- - ti i ni t t = l-n +i
-iln-i +i -i-i t =n-ii ~lil+i + ni-i +i -in t= l-n n l+i i-i t
t = + l-n + ,ii ~lil+i +i (-i -i +i l-ii i l+i ni t l=+i i nin+ = ai- +i-i +la- t =
-<i. ~lil+i + ln A
r
H+i ni-
C(n+i:) +
2
1
O
2
(g) CO(g)
:=+i ni-i inin+ = +la- t l--- <i ~lil+i~i + ,ii A
r
H+i niai- + =+- t
C(n+i:) + O
2
(g) CO
2
(g) A
r
H
1
CO(g) +
2
1
O
2
(g) CO
2
(g) A
r
H
2
tni n = < =i ~lil+i ii-
C(n+i:) +
2
1
O
2
(g) CO(g)
+nzi, A
r
H = A
r
H
1
A
r
H
2
Ex. l-- <i ~lil+i +i -ni +i ni-i l+l
F
2
O(g) + H
2
O(g) O
2
(g) + 2HF(g)
F
2
O(g), H
2
O(g) -ii HF (g) +i =i- -ni +nzi 5.5 kcal, 57 kcal -ii 64 kcal t
Sol. l<i t
(i) F
2
(g) +
2
1
O
2
(g) F
2
O (g); AH = 5.5 kcal
(ii) H
2
(g) +
2
1
O
2
(g) H
2
O (g); AH = 57 kcal
(iii)
2
1
H
2
(g) +
2
1
F
2
(g) HF (g); AH = 64 kcal
F
2
O-ii H
2
O(i) -ii (ii) = -ii <i n: =n-i =ni. n ll- ~i -l-i- t . l+ HF =ni+i (iii) n -ii <i n:
=n-i =ni. n =ni- ~i t := +i tn +t =+- t l+
[ =ni. (i) =ni. (ii) + 2 =ni. (iii) ] tn i-- ti-i t
F
2
(g)
2
1
O
2
(g) H
2
(g)
2
1
O
2
(g) + H
2
+ F
2
(g) F
2
O (g) H
2
O(g) + 2HF(g);
AH = 5.5 ( 57) + 2 ( 64)
i F
2
O (g) + H
2
O (g) O
2
(g) + 2HF(g); AH = 76.5 kcal.
<ra +t y-ist {<ra +t ai) (ENTHALPY OF COMBUSTION)
t t -ni l- - (+ ni n i ln+ ~iz+ ~i+=i- +i nizii = = +- ti + --+i -iii ~-ii + -i<
-i- t
-<iti + ln ni- +i 298. K ni-+ <t- -ni 890 kJ nin
1
t t l--- ~lil+i -i- t
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O() AH = 890 kJ mol
1
298 K ni- +i ni-+ <t- -ni l--- +i lnii i =+-i t
AH
c
(CH
4
, g, 298 K) = 890 kJ mol
1
23
CHEMISTRY
<t- +i (-ini +i =--i( vi nin+ = l-iil- + =+- t
:= v+i ~i+i +i =ti-i = . i ln+ + =-i- +i (-i ni +i l-ii i + =+- t ~-ii < = -i+ = :=+i
ni-i +la- i ~=-i t CH
4
+ =-i- +i (-i -i
C(n+i:) + 2H
2
(g) CH
4
(g)
== tn C -ii ti:i- +i = i- -i = -ti ti -i t . -ii <=i l< -i< --i t -i ~l--n -i< i
= n i- + =-i- +i (-i ni +i n i- + <t- +i (-i ni + nin = ~v-i = l-+in =+- t
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O()
AH
C
(CH
4
, g) = AH
f
(CO
2
, g) + 2AH
f
(H
2
O , ) AH
f
(CH
4
, g)
:=ln( AH
f
(CH
4
, g) = AH
f
(CO
2
, g) + 2AH
f
(H
2
O , ) AH
C
(CH
4
, g)
CO
2
-ii H
2
O+ =-i- +i (-i ni +i +i - -ii ti: i - + <t- + ,ii vi nin+ = = ai- + =+- t
:= v+i AH
C
0
(CH
4
, g) + nil- ni- + ,ii CH
4
+ =-i- +i (-ini +i ni-i +i i-i t t ni- t
AH
f
(CH
4
, g) = AH
f
(CO
2
, g) + 2 AH
f
(H
2
O , ) AH
C
(CH
4
, g)
= [ 393 + 2 (285) (890)] kJ mol
1
= 73 kJ mol
1
i -i-i i=il-+ =ni+ii +i i+ tn := vi-- + =+- t
C(n+i:) + O
2
(g) CO
2
(g) A
C
H = 393 kJ mol
1
2 [H
2
(g) +
2
1
O
2
(g) H
2
O()] A
r
H = 2( 285) kJ mol
1
[CH4(g) + 2O
2
(g) CO
2
(g) + 2H
2
O()] A
r
H = ( 890) kJ mol
1

C(n+i:) + 2H
2
(g) CH
4
(g) A
f
H = 73 kJ mol
1
<ra y-ist {ai) +i isa (MEASUREMENT OF ENTHALPY OF COMBUSTION) :
l+=i ii ai- < ni- + i ln+ +i <t- +i -ni +i =ini- < -in + izi (:= i - + ni ini +t- t ) n ni-
l+i i-i t i l+ nnin 30 i <i ~i+=i- = ii ti -i t + ni ini ai- < ni- + n = lii ti -i t
t =- i ii ln+ -ii (+ lnln- ~ii ,ii lii ti -i t i +i -ni +i it = ~ < -ii - zi = it i-
+i i +-i t = +i l-zi n <zii i ni t <ii + -n - +i l - -i+ ,ii nii i-i t -ii <t- ~lil+i +ii
i-i t l-+n- ini -ni n -ii +niini +i -i ci- + -in n ~i-i t
Toy u r kj
foy ksMd
r ki eki h
foy fxr v koj . k
d Sy ksj hehVj
t y
uewuk r ' r j h
ckWEc
ngu "ek dsfu/kkZj . k dsfy , ckWEc dSy ksj hehVj
l< + ni i ni -ii =ii = na-i +i + n -ni iil-i = C, -i n lz = AT - l-+n- ini -ni = q = CAT t
-ni < ni- m+ +ii t l< <ii 1 ni n ti - l-+n- ini -ni =
q
m
M
|
.
|
\
|
= AE
C
c (l-lz-- ~i-- ~lil+i)
~ AH
C
+i l--- +i = ni-i +i i =+-i t AH
C
= AE
C
+ An
g
RT ti An
g
<t- l+i +i = - ln- i=il-+
~lil+i n n=i -i=i + ==ni+ilnl- =i n l- - t
24
CHEMISTRY
Ex. 4 ni (iini- -ii n i - +i lni 25C-i <t- +- 6 ni. CO
2
n= --- +-i t (+ ni n = lni
+i ni- n+- -i +i nizii ai- +il (iini- -ii ni- +i <t- +i -ni 25C +nzi 1464 -ii
976 kJmol
-1
t
Sol. + O
2
CO
2
+ H
2
O
x lit. (4 x)lit. 6 lit.
(say)
or x nin (4 x) nin 6 nin
C nii + ln POAC nni-
2 x + 1 ( 4 x ) = 1 6; x = 2 lit.
:= +i C
2
H
4
+i ~i-- = 2 lit. -ii CH
2
+i ~i-- = 2 lit.
1 ni lni n C
2
H
4
+i ~i-- =
4
2
= .5 lit.
ni lni n CH
4
+i ~i-- = 1 .5 = .5 lit.
C
2
H
4
-ii CH
4
+ ln( -ni i=i- ~lil+i t
C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O; AH = 1464 kJ
CH
4
+ 2O
2
CO
2
+ 2H
2
O; AH = 976 kJ
25C-i AH+ ni- l< t . = in tn 25C-i l+=i ii n = + 1 ni n +i ~i-- ai- +- t (ni-i l+
<i 1 atm t)
25C -i l-nin ~i-- =
273
298
22.4 = 24.4 ni
:= +i 0.5 ni C
2
H
4
+ <t- n --- -ni =
4 . 24
1464
0.5 = 30 kJ
-ii 0.5 ni CH
4
+ <t- n --- -ni =
4 . 24
976
0.5 = 20kJ
1 ni lni + <t- n --- +n -ni +i nizii = 30 + (20) = 50 kJ.
<i n: =i-< -i ln- +i =ni+ln- (-i ni. (-i ni l- - t ln + 1 n in +i lni+ +i l-lz-- nizii
n lnni+ :l-z- =i-<-i +i ln- -ii i-i t
1 ni n ln +i ~nn ~nn nizii + lni+ n lnni- ln- +i =ni+ln- (-i ni := v+i t:
HCl(g) + 10H
2
O() HCl (10H
2
O) AH
1
= 69.5 kJ mol
1
t -i-i t l+ 1 nin HCl n = +i 10 ni n i-i n lnnii i-i t -i n +- -i 69.5 KJ ti -i t < =i ~-
ni-
(i) HCl(g) + 25 H
2
O() HCl (25H
2
O) AH
2
= 72.3 kJ mol
1
(ii) HCl(g) + 40 H
2
O() HCl (40H
2
O) AH
3
= 73.0 kJ mol
1
(iii) HCl(g) + 200 H
2
O() HCl (200H
2
O) AH
4
= 74.2 kJ mol
1
(iv) HCl(g) + aq HCl (aq) AH
5
= 75.0 kJ mol
1
lni+ +i nizii - -ti +i i - ~li+ nizii +i =ni+i ni i-i t = =ni+i (iv)
n4ia +t ai {y-ist) (ENTHALPY OF HYDRATION)
~-i< ~i lzi+ = ~i< i ln+i +i ni - +i -ni t -ni l- - t t n +i ~iz+ nizii + =ii
= i n ++ - ni l- -iii i ln+ -i- t -<iti + ln + l + =-+ +i ni - l--- +i <lzi - l+i
i-i t
CuSO
4
(s) + 5H
2
O () CuSO
4
. 5 H
2
O(s)
:= +i +i ~lil+i n -ni +i --- ti-i nnin ~l-l- ti-i t :=ln( i.e. AH +i ni- +iin+ t
CuSO
4
(s) + 800 H
2
O() CuSO
4
(800 H
2
O) AH
r
= 68.743 kJ mol
1
CuSO
4
. 5H
2
O(s) + 795 H
2
O () CuSO
4
(800 H
2
O) AH
r
= + 10.125 kJ mol
1
ii- tn i-- ti -i t
CuSO
4
(s) + 5H
2
O () CuSO
4
. 5 H
2
O(s) AH
r
= 78.868 kJ mol
1
25
CHEMISTRY
n =i ~i- + lni+- +i (-ini
l+=i n =i ~i- + ti: i - +i (-i ni. t (-i ni l- - t 1 ni n n =i ~i- +i ni ~i- n n
+ ~ili+ n ii ni i-i t
l-ni- =i. H
+
(aq) + =-i- +i ni-+ (-i ni +i zi - + i lni i-i t
Cl
n =i ~i- + lni+- +i (-ini +i := v+i = v<lzi- +- t

Cl(g) + aq. Cl(aq) AH =
a<iutat+i +t ai {yist) (ENTHALPY OF NEUTRALIZATION)
-ni +i t l-+n- ini nizii (+ n in - -i + ~-n +i (+ n in - -i + -ii ,ii i - -<i=i- l+i i-i t
ii
(+ ~-n. -ii ,ii -<i=i- ti -i t - (+ ni n n + l-ni i n n +- -ni +i nizii -<i=i-i+i -ni +tni-i t
-<i=i-i+i +i (-i -i +i := v+i -i =+- t l+ 1 ni n H
+
ni ln- n 1 ni n OH
+ =ii lnn+ ~li l-

n -i- t
H
+
(aq) + OH(aq) H
2
O() AH= 57.1 kJ/mole = 13.7 kcal/mol
4i< ia 4i4 f-<
SA + SB + ln( -<i=i-i+i -ni +i ni- tnzii 13.7 kcal/mol ~ii 57.1 kJ/mol + i ti-i t
~- < = ~-n -ii = i n + ln( -<i=i-i+i -ni +i ni- 13.7 kcal/mol ~ii 57.1 kJ/mol = +n ti -i t
i4aa +t ai {y-ist) (ENTHALPY OF IONIZATION) :
+ii +i : < n ~-n i -ii l+=i n -ii i ~-n + =ii ~li+ - ti -i t - -ni 57.1 kJ/mol = +n n +-
ti -i t
( =i :=ln( ti -i t +i l+ t ~-n i -ii. ln- n i - ~il-- -ti ti - t + z ~lil+i -ni. < n ~-ni -iii
+ ~i-- n +in n ~i i-i t t -ni. ~i-- +i -ni ((-i -i) +tni-i t -<iti t
HCN + Na
+
OH
Na
+
+ CN
+ H
2
O A
r
H = 12.13 kJ mol
1
CH
3
COOH + Na
+
OH
Na
+
+ CH
3
COO
+ H
2
O A
r
H = 49.86 kJ mol
1
~i-- +i (-i -i +i l--- +i = nii- + =+- t HCN+ ,ii < n ~-n +i -<i=i-i+i ti -i t := <i <i
n -i =+- t
~i-- HCN H
+
+ CN AH
1
= x
-<i=i-i+i H
+
+ OH H
2
O AH
2
= 57.1 kJ/mole
:- <i <i +i i+ i =ni+i -i: i-i t
HCN + OH H
2
O + CN AH = 12 kJ/mole
l-z- ti
AH = AH
1
+ AH
2
AH
1
= AH AH
2
= [12 (57.1)] = 45.1 kJ/mole
< n ~-n i < n -ii + ln( ~i-- +i (-ini l--i ~li+ ti ni. ~-n i -ii ---i +ni ti ni
Ex. HCl +i NaOH= -<i=i-i+i +i (-ini 57.1 KJ/mol -ii NH
4
OH + ln( 51.1 KJ/mol t -i NH
4
OH +
li - +i (-i ni +i ni-i +i
Sol. l<i t
H
+
(aq) + NH
4
OH(aq) NH
4
+
(aq) + H
2
O() AH = 51.1 kJ/mole
-<i=i-i+i n <i < ln i =+- t
(i) ~i--
NH
4
OH(aq) NH
4
+
(aq) +OH(aq) AH
1
= ?
(ii) -<i=i-i+i
H
+
(aq) + OH(aq) H
2
O() AH
2
= 57.1 kJ/mole
:= +i AH = AH
1
+ AH
2
:=ln
AH
1
= AH AH
2
= 51.1 kJ/mol + 57.1 kJ mol
1
= 6.0 kJ/mol
26
CHEMISTRY
u+i +t ai {y-ist) (ENTHALPY OF TRANSITION)
= +ni +i (-i -i t -ni l-- t (+ ni n (+ ~ <= ~ n ll-- ti-i t
-<iti + ln C(n+i:) C(tii) AH
trs
0
= 1.90 kJ mol
1
l< C(n+i:) + O
2
(g) CO
2
(g) AH
C
0
= 393.51 kJ mol
-1
-ii C(tii) + O
2
(g) CO
2
(g) AH
C
0
= 395.41 kJ mol
1
ii- C(n+i:) C(tii) AH
trs
0
= 1.90 kJ mol
1
+isi +t ai {y-ist) (ENTHALPY OF PRECIPTION)
~-i i +i -ni t -ni l-- t 1 ni n ~-i --i t -<iti + ln
BaCl
2
(aq.) + Na
2
SO
4
(aq) BaSO
4
(s) + 2NaCl(aq) A
r
H
0
=24.27 kJ mol
1
Ex. 25
0
C ~lil+i + ln( AH
0
+i ni-i +i
Ag
+
(aq) + Cl(aq) AgCl(s)
l<i ni t A
f
H (Ag
+
, aq) = 105 kJ mol
1
, A
f
H (Cl, aq) = 167 kJ mol
1
-ii A
f
H(AgCl, s) = 127 kJ mol
1
t
Sol. ~lil+i + ln(
Ag
+
(aq) + Cl(aq) AgCl(s)
tn i- t
AH = A
f
H (AgCl, s) A
f
H(Ag
+
, aq) A
f
H(Cl, aq)
= [127 105 (167 )] kJ mol
1
= 65 kJ mol
1
i4a + faii +t ai {y-ist) (ENTHALPY OF FORMATION OF IONS) :
t -ni l-- 1 ni n nil- ~i-. :=+i ni-+ -iii -i ~-ii = -i-i t
Cl
2
(g) + aq Cl
(aq) AH
r
= AH
f
(Cl
, aq)
f-ri u, H
+
(nt4) +t ia+ uia ai +i zi-4 ia fn4i iai r+
tn <i =+- t +i H
+
(aq) + OH
(aq) H
2
O(l) A
r
H
0
= 57.1 kJ mol
1
:= ~lil+i + ln( AH
r
0
= AH
f
0
(H
2
O,l) {AH
f
0
(H
+
,aq) + AH
f
0
(OH
,aq)}
~- 25
0
C, -i tn i-- ti -i t
AH
f
0
(H
+
, aq) + AH
f
0
(OH
,aq) = AH
f
0
(H
2
O, l) AH
r
0
:= +i AH
f
0
(OH
,aq) = { 286.1 ( 57.1)} kJ mol

1
= 229.00 kJ mol
1
:- ~i-i +i = i- (-i -i zi , i ln+ ln- + H
+
OH ~i- -ii < = ~i-i + l-ni i +i = i (-i -i = i--
+ =+- t -i<iti + ln Na
+
+ l-ni i +i (-i -i NaOH+ ~--- -- -i + ln- +i (-i -i -ii l-ni i +i
(-i-i = nii- + =+- t
NaOH(s) + ~--- ---i in ln- + = i- + ln i=il-+ ~lil+i t
NaOH(s) + nH
2
O() Na
+
(aq) + OH(aq) A
aq
H(NaOH, s) = 44.50 kJ mol
1
-i+- ~lil+i + <i -i -+ i-i +i =ni- nizii -l-i- t <i-i (-i -i +i : +n iiin -ti <-i t ~-
A
aq
H(NaOH, s) = A
f
H(Na
+
, aq) + A
f
H(OH, aq) A
f
H(NaOH, s)
or A
f
H (Na+, aq) = A
aq
H (NaOH, s) A
f
H(OH, aq) + A
f
H(NaOH, s)
= [44.50 (229.99) + (425.61)] kJ mol
1
= 240.12 kJ mol
1
:=i +i = NaCl(aq) i HCl(aq) = Cl(aq) +i l-ni i +i (-i -i +i l-ii i + =+- t :=+i = -i II n ~ l+- l+i
ni t l+=i ~il-+ ~lil+i (-i -i n l- - :- ~il-+ (-i -i + = i- -ii i ln+ + = i- +i (-i -i
l-i +- t
27
CHEMISTRY
Ex. H
2
O(l) =-i- +i (-i -i 285 kJ mol
1
-ii (+ n ~-n -ii (+ n -ii + -<i=i-i+i +i (-i -i 55 kJ
mol
1
t OH ~i- + =-i- +i (-i -i +i t ?
Sol. l<i ni t
H
+
(aq) + OH(aq) H
2
O()
A
f
H 0 285 kJ mol
1
A
neut
H = A
f
H(H
2
O, ) A
f
H(OH, aq)
:= +i A
f
H(OH, aq) = A
f
H(H
2
O, ) A
neut
H
= [285 (55 )] kJ mol
1
= 230 kJ mol
1
Ex. 25C (+ ni n HCl n = +i ~li+ i-i n ii ni i-i t -i (-i -i l- - +i ni-i +i ~-ii n l- - t
HCl(g) + aq H
+
(aq) + Cl(aq)
l<i t : A
f
H(HCl, g) = 92 kJ mol1 and A
f
H (Cl, aq) = 167 kJ mol
1
Sol. ~lil+i + ln(
HCl(g) + aq H
+
(aq) + Cl(aq)
tn i- t
AH = AH(Cl,aq) A
f
H(HCl, g)
AH = [167 (92 )] kJ mol
1
= 75 kJ mol
1
ri y-ist (BOND ENTHALPIES) :
n =i i ln+ n -l-i- =ii +i i + li - = n =i ~-ii n n +- nii ~-ii ~ii n n+ l-ni i n ~iz+
~i =- -i +i i li - -i i (-i -i +t- t l+ i li - -ni t ~iz+ -ni t i (+ llzi i ln+
+ l< n i + li - n +in ~i-i t -<iti + ln O H i + li - +i (-i -i ~iil+ -izii +i + l-
l-i +-i t . ti = Hnii i+ ti -i t
-<iti + ln n ~i n H
2
O(g) H(g) + OH(g) AH
r
0
= 501.87 kJ mol
1
l+ ti: i+=i: n n+ n OH i +i -i - + ln( li-- -ni +i nizii +i ~iz+ ti -i t
OH(g) O(g) + H(g) AH
r
0
= 423.38 kJ mol
1
e
OH
i (-i -i +i -i +- <i -i ni-i + ~i =- = liili- l+i i-i t
e
OH
=
2
kJmol 38 . 423 mol 87 . 501
1 1
+
= 462.625 kJ mol
1
l,niii ~i = H
2
+i l-il- n . i -ni i l i- (-i -i + =ni- ti -i t +il+ + li - l---
~lil+i +i in- +- t
H
2
(g) 2H(g) e
H H
= AH
r
0
= 435.93 kJ mol
1
:= +i. l+=i nii n + ln( <i n: i -ni ~i ~i +i l-lz-- = i + ln( i li - -ni + ni- +i ~i =-
+ n <i i-i t l-n nii + n -l-i- ti- t
ri aii u y+ fif+4i + fny fif+4i ai +i sf+na
ni-i +i n =i ~lil+i + ln( (-i -i l- -
C
2
H
4
(g) + HCl(g) C
2
H
5
Cl(g) (g)
AH =
|
|
|
.
|
\
|
|
|
|
.
|
\
|
ek "
d ; vko' fy, ds cnyus
sa ijek.kqq e dk xSlh; mRiknksa
ek " d ; vko' fy, ds
cnyus .kqq esa xSlh; ijek
dk xSlh; vfHkdkjdks
= [4e
CH
+ e
C=C
+ e
HCl
] + [5e
CH
e
CC
e
CCl
]
= (e
C=C
+ e
HCl
) (e
CH
+ e
CC
+ e
CCl
)
28
CHEMISTRY
Ex. -i- l< n -i (-i ni + ni-i +i -in + ~lil+i + ln( (-i ni l- - +i ni-i +i
C
2
H
4
(g) + H
2
(g) C
2
H
6
(g)
uai ~i+ -i (-i ni
C C 336 kJ mol
1
C = C 606 kJ mol
1
C H 410 kJ mol
1
H H 431 kJ mol
1
Sol. l-zii-=i. tn =ni+i +i l--- v+i = v<lzi- + =+- t
-ii n =i nii n -i - + ln( ~iz+ -ni +i ~iz+-i
-i- + ln 1 C = C 606 kJ mol
1
-i- + ln 4 C H 4 x 410 kJ mol
1
-i- + ln 1 H H 431 kJ mol
1
+ n 2677 kJ mol
1
:= +i AH = 2802 kJ mol
1
+ 2677 kJ mol
1
= 125 kJ mol
1
Ex. -i- l< n -i (-i ni + ni-i +i -i n + n =i ~i:=i vi- + =-i- +i (-ini +i ni-i +i
3
2 2
CH
|
CH CH C CH = =
u ai C H -i +i -i (-i ni
C C -i +i -i (-i ni
C= C -i +i -i (-i ni
+i- + -i -- +i (-ini (n +i:)
H
2
(g) + li - +i (-i ni
Sol. ~i:=ivi- + ln(. tn l--- i- t
2C C -i. 2C= C -i -ii 8C H -i
l=n -i n +- ti -i t
[2(347.69) + (615.05) + 8(413.38)] kJ mol
1
= 5 232.52 kJ mol
1
-il+ AH (n =i nii ~i = )
:== =-l-i- ~lil+i
5C(g) + 8H(g) C
5
H
8
(g) A
f
H
1
= 5232.52 kJ mol
1
-- := ~lil+i = =-l-i- A
f
H +i ni- l--- ti ni
5C(n+i:) + 4H
2
(g) C
5
H
8
(g) A
f
H = ?
:= l--- i--i = vi-- + =+- t
5C(g) +8H(g) C
5
H
8
(g) A
r
H
2
= 5232.52 kJ mol
1
5C(n+i:) 5C(g) A
r
H
3
= 5 718.39 kJ mol
1
4H
2
(g) 8H(g) A
r
H
4
= 4 435.97 kJ mol
1
29
CHEMISTRY
:-+i i- . tn vi-- +- t
5C(n+i:) + 4H
2
(g) C
5
H
8
(g) A
f
H = 103.31 kJ mol
1
nil+ = ni-i +- l--- vi-- ti -i t
4
f
AH
4
5C(g) + 8H(g)
CH
3
CH = C CH (g)
2 2
5C(graphite) + 4 H (g)
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
CH = C CH (g)
2 2
2
A
f
H
5
f
AH
3
2 2 8 e e
C=C C C
e
CH
t = + l-n + ~-=i. tn vi-- +- t
A
f
H = 5AH
3
+ 4AH
4
2e
C = C
8e
C H
= (5 x 718.39 + 4 x 435.97 2 x 615.05 2 x 347.69 8 x 413.38) kJ mol
1
= 103.31 kJ mol
1
Ex. l--- ~i+i = -i +i S S -i (-i ni +i ni-i +i
C
2
H
5
S C
2
H
5
(g) A
f
H = 147 kJ mol
1
C
2
H
5
S S C
2
H
5
(g) A
f
H = 201 kJ mol
1
S(g) A
f
H = 222 kJ mol
1
Sol. l<i ni
(i) 4C(s) + 5H
2
(g) + S(s) C
2
H
5
S C
2
H
5
(g) A
f
H = 147 kJ mol
1
(ii) 4C(s) + 5H
2
(g) + 2(s) C
2
H
5
S S C
2
H
5
(g) A
f
H = 201 kJ mol
1
Eq. (ii) +i Eq. (i) = ii-
C
2
H
5
S C
2
H
5
(g) + S(s) C
2
H
5
S S C
2
H
5
(g) A
f
H = 54 kJ mol
1
:= i- l--- =ni+i i-- ti-i t
S(g) S(s) A
f
H = 222 kJ mol
1
tn i-- ti-i t
C
2
H
5
S C
2
H
5
(g) + S(g) C
2
H
5
S S C
2
H
5
(g) A
f
H = 277 kJ mol
1
S S -i -- + +ii 277.49 KJ +i -ni n +- ti -i t
:=ln( S S -i +i -i (-i -i 277 KJ/Md t
l-zii-=i. tn l--- ni-i +i v<lzi - + =+- t
4C(g) + 10H(g) + S(g) + S(g)
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
H(g) + S(s)
AH
H
|
C
|
H
H
H
|
C
|
H
S
H
|
C
|
H
H
|
C
|
H
S H(g)
2 + 10
+
e
C C C H
e
e 2
C S
A
vap
H(S) -2 - 10
-
e
C C C H

e
e e 2 -
C S S S
H
C
H
H
H
C
H
S
H
C
H
H
C
H
S H
ru + fa4 + aui
AH
0
= -i li - = =-l-i- (-i ni -i -- = =-l-i- (-i ni
= [2e
C C
+ 10e
CH
+ 2e
CS
+ D
vap
H(S)] + [2e
CC
10e
CH
2e
CS
e
SS
]
= A
vap
H(S) e
SS
or e
SS
= A
vap
H(S) AH
= A
vap
H(S) [A
f
H(C
2
H
5
S S C
2
H
5
] A
f
H(C
2
H
5
S C
2
H
5
)]
= [222 {201 (174)}] kJ mol
1
= 277 kJ mol
1
30
CHEMISTRY
aai<t ai (RESONANCE ENERGY) :
AH
~--i<
= AH
f, ii ln+
AH
f, =zil--+
= AH
c, =zil--+
AH
c, ii ln+
Ex. l--- ni-i (l+n-i) +i =ti-i = -i- +i =i- -ni +i ni-i +il ni-i +i +i: ~--i< -ti t
i -i C C = 83 kcal
C C
= 140 kcal ; C H = 99 kcal
C siit+i +t ai = 170 .9 kcal
H +t sit+i ai = 52.1 kcal
Sol. tn l--- ~lil+i + ln( AH+i niai- +-i t
6C (s) + 3H
2
(g) C
6
H
6
(g)
C
C
C
C
C
C
AH = ?
~li+i+i + ln(
6 nin C + nii+i +i -ni = 6 170.9 kcal
6 nin H + niii+i +i -ni = 6 52.1 kcal
-i<i + ln(
6 nin C Hii +i =i- -ni = 6 99
3 ni n CC ii +i =i- -ni = 3 83
3 nin
C C
ii +i n =i- -ni = 3 140
i n +- tn C
6
H
6
, +i = i- -ni ti-i t
AH = 6 170.9 + 6 52.1 6 99 3 83 140 = 75.0 kcal
ai aii fif+4i ai u-ri (RELATION BETWEEN ENERGY AND ENTHALPY OF A REACTION)
A
r
H = A
r
U + (Av
g
)RT
ti Av
g
= ~li+i+ = -i< n i- ini n =i -izii + ==ni+i lnl- = i~i n l-- t ~lil+i
+ Av
g
+i ni-i +i i-i t - t i- < -i -ilt . +i ~lil+i + + n n =i = na+i + ==ni+ilnl- +i = i~i
+i ln-i i-i t l+ ai= -ii < i - -n ni-i i-i t
f+i+ ut+i
(AH
0
+i l- - -i + =ii)
- l + <ii +i (-i -i (ni-+ (-i -i). <ii +i ~-ii l-i +-i t (+ <ii +i (-i ni +i ni- =n + =ii
ll- - ti -i t . -ii ~lil+i +i (-i ni n l- - ii -i l-i +-i t . l= ~lil+i +i: i-i t
(-i ni l-- (i AE l= l-- ~i-- ~lil+i +i: i) +i l+-i+ =ni+i + ,ii v<lzi - +- t
oP + |Q R + oS
-i T t ~lil+i +i ni-+ (-i ni AH
1
0
t -
AH
1
= H
m
(R,T
1
) + oH
m
(S, T
1
) oH
m
(P, T
1
) |H
m
(Q, T
1
)
-i T
2
:=+i + =ni- ~lil+i +i: i-i t
AH
2
= H
m
(R,T
2
) + oH
m
(S, T
2
) oH
m
(P, T
2
) |H
m
(Q, T
2
)
- (-ini n l- - (<i -i -i (-ini n l- -)
AH = AH
2
AH
1
= {H
m
} (R,T
2
) H
m
(R,T
1
)} + {H
m
} (o,T
2
) H
m
(o,T
1
)}
o{H
m
} (P,T
2
) H
m
(P,T
1
)} - | {H
m
} (Q,T
2
) H
m
(Q,T
1
)}
H
m
(R, T
2
) H
m
(R,T
1
) =C
P, R
(T
2
T
1
) =l-- <i 1 ni n ~li+i+ + -i +i T
1
= T
2
-+ ci- + ln( ~iz+
-i +i nizii
:=i +i
H
m
(S,T
2
) H
m
(S,T
1
) = C
P,S
(T
2
T
1
)
H
m
(P,T
2
) H
m
(P,T
1
) = C
P,P
(T
2
T
1
) -ii H
m
(Q,T
2
) H
m
(Q,T
1
) = C
P,Q
(T
2
T
1
)
:=ln(
AH = AH
2
AH
1
= C
P,R
(T
2
T
1
) + C
P,S
(T
2
T
1
) o C
P,P
(T
2
T
1
) + C
P,Q
(T
2
T
1
)
= [ C
P,R
+ oC
P,S
o C
P,P
|C
P,Q
] (T
2
T
1
)
= AC
P
(T
2
T
1
)
AC
P
= C
P, R
+ oC
P,S
oC
P,P
|C
P,Q
= ~li+i+ -ii -i< +i nin -niiil-i n ~--
31
CHEMISTRY
:=ln( AH
2
= AH
1
+
}
A dT . C
P
~lil+i + ln( -<iti
N
2
(g) + 3H
2
(g)

2NH
3
(g)
AH
2
= AH
1
+ AC
P
(T
2
T
1
)
ti AC
P
=
2 2 3
H , P N , P N , P
C 3 C C 2
* l-- ~i-- +i ~lil+i + ln(
}
A + A = A dT . C E E
V
0
1
0
2
ainfa+t +i II
nd
fa4
~iz+-i =nni- + ln( I
st
l-n ~i -- t
-<i=i-i+i + +i nn-i+ > 0
<t- i-i +i ltni + < 0
i-i +i ln-i i-i +i +i-i+> 100 C
nn <ii +i ai +-i. n = +i n +- v=i. n =i +i lni
--vi+l-+~-+nii vl+i
l< (+ --zi - ti ~-i l<zii n l+=i ii l zi + l-i l+=i i +i+ + nl- +-i t -i := l<zii +i --
l<zi +t- t -ii := v+n +i -- v+n +t n
=ini
vin l-n + ,ii l+=i v+n +i l<zii ai- -ti + =+- t -- v+l- n l-lz-- ll-il- n (+ v+n +i
llzi l<zii ti -i t
1. -i +i+ -iii +i vi-- +- + ln(
* =ii -ni-i i ~lil+i -- t
* =ii -nizii ii ~lil+i ~-- t
~i<
* l + +i nn-i+. (0C = -) il AH > 0 , AE > 0
* i-i +i ii+i. (100C = -) AH > 0 , AE > 0
* i-i n -iti +i +n-i. AH = 0 , AE = 0
* 0 , AE > 0
* t < ii ni l+ v+l- -i -ii <ii +i i (i< l-z+) = viil- +-i t
-ninl-+i +i l,-i l-n
i +i (-ii l-- = c-i t
AS
i
= AS
--zi
+ AS
lzi
-- vl+i + ln(
ti (s) = (- ii ~-ii i i< l-z+-i +i ni- t t ~-ii +n- t -ii niziin+ n i t
nli-i =
ds =
T
dq
rev
or AS =
}
T
dq
rev
dq (+ ~-ii +n- t i + n -+nii vl+i + ln( t
dS dq
rev
, dS
T
1
--- T . (- ii tn = ti ~li+ t :=ln( -ni +i -i (- ii n ~li+ l- - -ti +-i t
y-aist niai
AS
l zi
+i ni-i l< l zi ~--- -ni +i n -i t -i := +i -ni +i nizii l zi +i < - t -+nii
= ti +-i t
AS
lzi
=
}
T
dq
k ifjos'
32
CHEMISTRY
l zi + ln( T l-- t
AS
lzi
=
T
1
}
k ifjos'
dq
=
T
q
k ifjos'
-i + =-ii + l-n =
q
lzi
= q
--zi
AS
lzi
=
T
q
k rU>
For AS
--zi
S (+ ~-ii +n- t. AS i l-i -ti +-i t
AS
~--+nii
= AS
-+nii
AS =
}
B
A
rev
T
dq
-+nii i
e.g. Cu ni+ +i in i-ii n ii i- t
AS
universe
= AS
system
+AS
surr
= } }
+
T
dq
T
dT . s . m
surr
T
T
2
1
AS
universe
= m.s. n
1
2
T
T
+
2
surr
T
q
n l+- q
surr
= q
system
= ms (T
2
T
1
)
= ms (T
1
T
2
)
AS
universe
= ms n
1
2
T
T
+
2
2 1
T
) T T ( ms
> 0
e.g. <i-i +i ni+ n t
Cu (M)
T
1
T
2
Thermostart
/////////////////////////////////////
/////////////////////////////////////
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
T
1
> T
2
AS
system
= AS
A
+ AS
B
=
}
T
dq
A
+
}
T
dq
B
=
} }
+
B
2
A
1
dq
T
1
dq
T
1
33
CHEMISTRY
AS
system
=
2
B
1
A
T
q
T
q
+
if q
A
= q
q
B
= q
AS
system
=
0
T
q
T
q
2 1
>
sf+4i + -ana i<zi nu + fny y-aist +t niai
~-ii A
irr
S
irr
A

~-ii B
P
1
, V
1
, T
1
P
2
, V
2
, T
2
ti s ~-ii +n- t AS i l-i -ti +-i t
AS
irrev
= AS
rev, system
=
}
B
A
rev
T
dq
-+nii i
in l-n =
du = dQ + dw
dQ = du dw
-+nii i + ln(
dq = dq
rev
dQ
rev
= du + P
gas
dv {P
ext
= P
gas
-+nii }
AS
rev
,
system
=
}
+
B
A
gas
T
dv P du
~i<zi n = + ln(
V
nR
T
P
gas
= & du = nc
V
dT
AS
sys
= } }
+
2
1
2
1
V
V
T
T
v
V
nRdv
T
dT nc
AS
system
= nc
v
ln
1
2
T
T
+ nR ln
1
2
V
V
uaist4 sf+4i
(a) a-+it4
~-ii A

v Re
~-ii B
P
1
,V
1
,T P
2
,V
2
,T
AS
system
= nC
V
ln
1
2
T
T
+ nRln
1
2
V
V
+
0
AS
sorrounding
=
T
dq
system
FLOT du = dq + dw
dq = dw
q = w as w = nRTn
1
2
V
V
q = nRTn
1
2
V
V
34
CHEMISTRY
AS
sys.
=
T
V
V
n nRT
1
2

= nRn
1
2
V
V
AS
universe
= AS
system
+ AS
surr
= nRn
1
2
V
V
nRn
1
2
V
V
= 0
(b) a+it4
~-ii A

irrev
~-ii B
P
1
,V
1
,T P
2
,V
2
,T
AS
system
= nRn
1
2
V
V
AS
Surrounding
=
T
q
system
q
system
+i ni-i FLOT ,ii +i i-i t
q
system
= P
ext
(V
2
V
1
)
AS
surrounding
=
T
) V V ( p
1 2 ext

AS
universe
= nRn
1
2
V
V
T
) V V ( p
1 2 ext

> 0
=
T
1
irrev rev
1 2 ext
1
2
) wgas ( ) wgas (
) V V ( P )
V
V
n nRT (
(

~-+nii n= +i +i -+nii +i +i ~-ii +n t
=&i sf+4i
(a) a-+it4 =&i
~-ii A

rev
~-ii B
P
1
,V
1
, T
1
P
2
,V
2
, T
2
AS
system
= nC
V
n
1
2
T
T
+ nR n
1
2
V
V
TV
1
= l--
1
2
T
T
=
1
2
1
V
V

|
|
.
|
\
|
(AS)
system
= nC
V
n
1
2
1
V
V

|
|
.
|
\
|
+ nRn
1
2
V
V
= 0
AS
surr
=
T
q A
= 0
AS
universe
= 0 + 0 = 0
(b) a-+it4 =&i
~-ii A

irre
~-ii B
P
1
,V
1
,T
1
P
2
,V
2
,T
2
~- +nii zi n l+i n t =ni- ~-ii B-+ -ti t --i t t + n -+nii zi n ,ii t --i
t
AS
system
= nC
V
n
1
2
T
T
+ nr n
1
2
V
V
> 0 [(T
2
)
irrev
> (T
2
)
rev
]
35
CHEMISTRY
AS
surr
=
T
q
sys
= 0 as q = 0
~- +nii =i + ln( -i n +ni +n ti -i t :=ln( +i ii +n l+i i ni :=ln( ~- +nii =i
+i ll-il- n -i n +ni + +ii (- ii +n ti -i t ~- + n (- ii c ni
Ex. (a) 25C -i (+ ni n ~i<zi n =. =n-ii -ii -+nii = ~i-- 10 ni = 20 ni ~i-- -+
=il- ti -i t
(i) n= +i (- ii l-- +i t ; (ii) n = ,ii l+i ni +i t ; (iii) q
(l zi)
+i t ?
(iv) lzi +i (-ii l-- +i t ; (v) lzi -ii -zi +i (-ii l-- +i t
(b) -i +i+ +i iin < -ii n= +i 10 ni ~i-- in l-il-- - n i- < := ll-il- n ii -+-
z-i + --i <il(
Sol. (a) (i) AS = 2.303 nR log
1
2
V
V
= 2.303 1 8.314 log
10
20
= 5.76 J/K.
(ii) W
rev
= 2.303nRT log
1
2
V
V
= 2.303 1 8.314 298 log
10
20
= 1781 J.
(iii) =n-ii +n + ln( AE = 0 -ii n = ,ii ~zii li- -ni t
q
rev
= AE W = 0 (1718) = 1718 J.
q
rev
= 1718 J. ( +n -+nii t )
(iv) AS
surr
=
298
1718
= 5.76 J/K.
:= +i - zi +i (- i i 5.76 J = c i-i t -ii l zi +i (- i i 5.76J, = i i-i t := +i +n
-+nii ti ni
(v) AS
sys
+ AS
surr
= 0..... -+nii +n + ln(
(b) (i) AS = 5.76 J/K, i +i =ni- t ni +i l+ S (+ ~-ii +n- t
(ii) W = 0 ( p
ext
= 0)
(iii) lzi + =ii +i: -ni -ii-i--i -ti ti -i t
(iv) AS
surr
= 0.
(v) - zi -ii l zi +i (- i i 5.76J/K, = c i-i t ~- tn +t =+- t +i ~- +nii +n n (- i i c -i t
fif+4i + fny
aA + bB cC + d
AS
0
system
= (E n
i
0
m
S )
product
(E n
i
0
m
S )
reactant
ti
0
m
S = ni-+ nin (-ii :=ln( :=+i ni-i -ninl-+i + --i l-n = +i i-i t
AS
surr
=
T
Q
system
=
T
H
system
A
* 0 K, i = l+-ni <ii + ln( (-ii = 0
ii sfaa + fny
AS
nn-
=
} }
= =
T
Q
dq
T
1
T
dq
l-- <i + ln( AS
nn-.
=
T
H
fus
A
l-- ~i-- + ln( AS
nn-.
=
T
U
fusion
A
36
CHEMISTRY
AS
vap
=
} }
= =
T
Q
dQ
T
1
T
dQ
l-- <i + ln(, AS
vap
=
T
H
vap
A
l-- ~i-- + ln(, AS
vap
=
T
H
vap
A
fn-u a ai (G)
(+ --zi +i+ ~lil+i +i -- zi-i +i -i-i t l= ln= + ,ii -ii ni ii :=ln( l zi + ln( (- i i
+i ni-i +i ~iz+-i -ti ti -i t
AS
universe
= AS
system
+ AS
surrounding
AS
surr
=
T
Q
system
=
T
H
system
A
TAS
univ
= TAS
system
AH
system
-i -ninl-+i +n- G= ln= n +- -i (~-ii +n- -ii (+ niziin+ n i)
G
system
= H
system
TS
system
AG = AH TAS
AG
system
= AH
system
TAS
system
.................. (ii)
=ni+i (i) (ii) n -n-i +-
AG
system
= TAS
universe
aiai +t a4t sffifa
(i) If AG
system
is (ve) < 0 +n -- t
(ii) If AG
system
is > 0 +n ~-- t
(iii) If AG
system
= 0 +n =i- t
:=ln( + -i AG
=
0
AG
system
AS
system
AG
system
= AH
system
TAS
system
+ Ve Ve +
Ve + Ve
+ Ve + Ve Ve --- -i
Ve Ve + Ve --- -i
AG = ni-+ n+- -i l-- :
l+in+ l+=i ni-+ ll-il- n -i< n ll-- ti- t -i n +- -i l- - +i AG +t- t (-)
t 1 i 1 nin + ln( <i n: t
ia+ sffifa s
AG = AH TAS
= <i n: ~lil+i + ln( l--
o A + |B

C +
o
D
AG = (-i< +i ln= -i) (l+i+i+ +i ln= -i)
AG =
0
C , m
G +
0
D , m
G o
0
A , m
G o
0
B , m
G | , ti
0
m
G -ii
0
m
H +i ni-i -ti + =+- t
:=ln( <ii + l-ni i +i ln= -i n := =--i +i ll-- + =+- t l-nii +i ni-+ ln= -i
AG =
0
C , f
G A +
0
D , f
G A o
0
A , f
G A o
0
B , f
G A |
0
f
G A : l-nii +i ni-+ ln= -i
37
CHEMISTRY
- l< ni-+ ~-ii n t -i
0
f
G A = 0
AG =
0
product , f
G A
0
ts tan reac , f
G A
~lil+i +i nl- + ln(
AG = AG + RT n Q
Q ~lil+i nii+, AG > 0 z-l<zii n ini, AG < 0 ~n l<zii n
=i-i-ii AG= 0 Q = K AG = RT n K
Ex. 25C -i CH
3
COOH + ln( K
a
1.754 10
-5
t 50C K
a
1.633 10
-5
t CH
3
COOH + ~i-- + ln(
AH -ii AS + ni- +i t ?
Sol. (AG)
298
= 2.303RT log K = 2.303 8.314 298 log (1.754 10
-5
)
= 27194 J.
(AG)
323
= 2.303 8.314 323 log ( 1.633 10
-5
)
= 29605 J.
AG = AH TAS
27194 = AH 298 AS .......... (i)
29605 = AH 323 AS .......... (ii)
AH = 1.55 kJ/mol ; AS = 96.44J/mol.K
ai nfa+t +i a at4 fa4 (THIRD LAW OF THERMODYNAMICS) :
-i + nzi - ni- =ii zi z -i i ln+i + i l+-n +i (- ii zi- ti -i t
:= +i l+=i ii zi z <ii + ln( l+=i ii l< n -i (- i i + zi z ni- +i ni-i +i i =+-i t ((-i -i
+ ~ni- n ni- )
ni-+ ~-ii n (298 K, 1 atm) t ni-+ (-ii S t
:-+ ni- =iii z t : AS = E S
-i<
E S
~li+i+
MISCELLANEOUS SOLVED EXAMPLES
1. "a" + <i n -i +i t nizii ai- l+l. i l+ <ii + -i n 3 K = 5 K -+ lz +- + ln( ~iz+ t
+n -i C
P
= aT
3
t
Sol. q =
}
dT ncp
=
}
dT naT
3
= na
5
3
4
4
T
(
(
=
4
na
[(5)
4
(3)
4
]
=
| |
4
81 625 na
q = 136 na. Ans.
2. 0C -i (+ -ni lnln- (+ izi n 100 g n ii t 0C-i n + - +i i +i it
l-+in lni i-i t . - + z n n i-i t -ii + z ii+ - ti i-i t izi n n zi i -ti t-i t . -
-- ini + + ii +i ni-i l+l 0C-i n + ii+i +i n -- -ni = 2.10 x 10
6
J/kg -ii + +
nn- +i n-- -ni = 3.36 x 10
5
J/kg t
38
CHEMISTRY
Sol. n +i +n <ni- = M = 100 g
0C n +i ii+i +i n-- -ni
= L
1
= 21.0 x 10
5
J/Kg
= + + nn- +i n-- -ni = L
2
= 3.36 x 10
5
J/Kg
ni-i. + +i -- ini <ni- = m
-i. n +i ii+- <ni- = M m
n +i + n -- + ln( ni n: -ni = mL
2
~- . mL
2
= (M m) L
1
or m = 86 g [Ans. 86.2 g]
3. (+ l-- in <i 2.1 i nn + lz (+ ~i<zi n = + 4 ni = 6 ni -+ =i n l+ n +i +i -i n
293 K 1 nin n +i nn +- n l+i i-i t l< n +i llzi -ni 4.2 J g
1
K
1
t -i n +i ~l--n
-i +i t ?
Ans. 299 K
Sol. w = 2.1 [6 4]
= 2.1 2
= 4.2 atm lit.
= 4.2 101. 325 J
t +i n +i -ni <i- +- + ln( in n lni ni
llzi -ni H
2
O= 4.2
. K gram
J
1 ni n + ln(
= 4.2 18 (
K Mole
J
= 4.2 18 (
K mole
J
= 75.6
4.2 101.325 = 75.6 [T 293]
5.63 = T 293
T = 299 K
4. 0C -ii 4.6 mm Hg <i 1 nin + l-- -i -ii <i ni n <n i-i t l< + + nn- +i n --
-ni 80 cal/g -ii 0C < + i- +i n-- -ni 596 cal/gram t ~i + +i ~i--. i-i (i) +i - n-i
n -n t -i AH -ii AE +i ni-i +i
Sol. nini +i =i = 1 nin
T = 273 K.
Pv = nRT.
760
6 . 4
v = 1 0.082 273
v = 3699 lit ~ [3700 lit]
nn- +i n-- -ni = 80 cal/gram ii+i +i n-- -ni = 596 cal/gram
AH = 80 18 + 596 18
= [80 + 596] 18
AH = 12168 cal
AH = AE P [V
2
V
1
]
12168 = AE +
760
6 . 4
[3700 1]
AE = 12168
760
6 . 4
3699 24.24 = 12168 540.71
= 12168 542.72 = 11627.28 cal.
Ans. 12168 cal, 11627.28 cal
39
CHEMISTRY
5. Ag + ln(
P
C (JK
1
mol
1
) 24 +0.006 T ,ii l<i ni t l< 1 i nn <i l=- + 3 ni n +i -i 27C
= 927C-+ cii i-i t -i AH+i ni-i +i
Sol. AH = }
2
1
T
T
P
dT C
= }
+
2
1
T
T
dT ) T 006 . 0 24 (
AH = 24 (T
2
T
1
) +
2
1
0.006 (
2
2
T
2
1
T ) Jmol
-1
For 3 mol, AH = 76950 Ans. 76950
6. l--- =--i +i -in +- t( 100 ml + < -i- + =-i <t- + ~--n- l-+n- ini -ni +i ni-i +i
(i) 18 g n+i: + =-i <t- n l-+n- ini -i 590 KJ t
(ii) 1 ni i-i + =ii ~i ~i +i H
2
-ii O
2
n li - + ln( ~iz+ -i 15889 KJ t
(iii) < -i- + =i- +i -ni +i ni-i 50 kJ/mol t
(iv) C
6
H
6
() +i i- = 0.87 gm/m t
Sol. (i) C(s) + O
2
(g) CO
2
(g) ;

f
H A = 393.33 KJ/mol
(ii) H
2
(g) +
2
1
O
2
(g) H
2
O () ;

f
H A = 286 KJ/mol
(iii) C
6
H
6
() +
2
15
O
2
(g) 6CO
2
(g) + 3H
2
O()
AH = [6(393.33) + 3 (286)] 50 = 3268 KJ
87 gm -i- = l-+n- ini -ni = 3645 KJ Ans.
7. 25C -ii 740 torr CH
4
(g) -ii O
2
(g) + 1 lni +i -n -i (+ + ni ini n l-- <i l+i +-i t . lni
+ =ii +ni ini +i -niiil-i 1260 cal/K t ni - + =- i <t- CO
2
-ii H
2
O -- + +ii +niini
+ -i n lz0.667 K t -i i--l+ lni n CH
4
+ ni n l-zi- +i ni-i +i AH
<t-
(CH
4
) = 215 cal mol
1
t
Sol. PV = nRT
=
760
740
1 = n 0.082 298
n = 0.04 mole
ni-i. nini +i = i
CH
4
= x & CO = (0.04 x)
CH
4(g)
+ 2O
2
CO
2
+ 2H
2
O
AH = c.dT
215 = n 1260 6.67
= n[840.42 cal]
n = 0.0255
CH
4
+ ni n = 0.2558
CH
4
+ nin l-zi- =
04 . 0
02558 . 0
100 = 63.95 Ans.
8. 25C -i =i:+nit +=- () ~i -i- () + l-nii +i ni-+ nin (-i-i +nzi 156 ~i + 49 KJ mol
1
t
25C -i =i:+ni t+=- + ti:i-i+i +i ni-+ (-i -i 119 kJ mol
1
t . l--- l< n ~i+i +i -in
+- t -i: l+ -i- +i ~- -i<i -i +i lnii +i tini
rn : 3- +i-+i- l,-i + (-i-i l-ni i
= AH
F
( ) A H
f
( )
= 156 (+ 49) kJ
= 205 kJ.
l<i ni t l+
40
CHEMISTRY
+ H
2
A ; H = 119 kJ
-i- n n 3 l,-i + (-i-i l-nii +i =zil--+ ni-
=3 (119) kJ
= 357 kJ.
-i- +i ~--i<i -i = 357 (205) kJ
= 152 kJ mole
1
9. l--- ni+ (+n=i +n +i <zii-i t. - l-+i ,ii l+i ni +i t
1
2 4
5
V(ltr)
P(atm)
(A) 9104 J (B) 202.6 J (C) 506 J (D) 101.3 J
Sol. (B)
0 2 4
V (Lit)
1
5
W = Pext (V
2
V
1
) = 1 2 101.325 J = 202.6 J
10. 2 kg tilnn + -n - +i (~i<zi ni-- t () ABC +n n lni i-i t -ii (+ ~nn -n - n =ni- 2 kg n = +i ADC
+n n +in n n- t - A-ii B ~-ii +i -i l--- tini (l<i ni R= 8.3 n/nin K) :
C B
D A
10
20V(m )
3
P
(
1
0
N
/
m
)
4
2
10
5
(A) T
A
= 120.5 K, T
B
= 120. 5K (B) T
A
= 241 K, T
B
= 241 K
(C) T
A
= 120.5 K, T
B
= 241 K (D) T
A
= 241 K, T
B
= 482 K
Sol. (C)
T
2
= 4T
1
P
A
V
A
= nRT
A
5 10 =
2
1000 2
0.082 TT
A
5
5
10 01 . 1
10 5 . 0
10 10
3
=
2
1000 2
0.082 TT
A
41
CHEMISTRY
01 . 1
1
= 0.082 TT
A
T
A
=120.5
l-i <i
B
B
A
A
T
P
T
P
=
T
B
=
5
10
P
T . P
A
A B
=
120.5 = 241 K.
11. n=i -n- + =n-ii =i n ti =i t ( IUPAC+ - l-ni-=i w(+i) +i l--t + =ii nil-)
[=ni- i li+ ~ l-n ~-ii~i + n -+nii ~- +nii +n = -- ti- t ]
(A) w
rev
> w
irrev
(B) w
irrev
> w
rev
(C) q
rev
< q
irrev
(D) ~-ni- -ti nni =+-
Ans. (B)
12. (+ nii + ~i<zi n = +i 1 ni n l-zi n <zii n -+ + ~- =i n -i t i abc + ~- l<zi n = a = c + ~- l<zi
=il- ti-i t -i ~i--l+ -i n l- - +i t
c
b
a
V
0
T
0
4V
0
2P
0
P
0
v k; r u
n
k
c
(A) 3 P
0
V
0
(B) 6 RT
0
(C) 4.5 RT
0
(D) 10.5 RT
0
Sol. (D)
v
0
4v
0
T
0
C
Volume
P
0
2P
0
P
r
e
s
s
u
r
e
a b
l-< C Pv = nRT
2P
0
4v
0
= 1 RT
C
T
C
= (
R
V P 8
0 0
l-< a
P
0
V
0
= 1 RT
0
T
0
=
R
V P
0 0
; T
C
= 8 T
0
~i--l+ -i n l-- = [nC
V
dT]
i a = b + ln(
= 1
2
3
R [3T
0
]
42
CHEMISTRY
=
2
9
RT
0
i b = c + ln(
1
2
3
R [4T
0
] = 6T
0
R
+n l-- =
2
9
RT
0
+ 6RT
0
=
2
RT 21
0
= 10.5 RT
0
.
~- ~i--l+ -i n +n l--
AU = 10.5 RT
0
13. n = +i (+ l-lz-- < ni- 1 atm + l-- in <i + lz (1L, 10 atm) = (4L, 5 atm) -+ =il- ti -i t l<
n = +i i li+ -i 300 Kt -ii +n +i -ni iil-i 50 J/Ct . - +n + <i i- (-i -i l- - ti ni (1L atm
~ 100 J)
(A) AH = 15 kJ (B) AH = 15.7 kJ (C) AH = 14.4 kJ (D) AH = 14.7 kJ
Sol. (B)
AH = AE + A(PV) & AE = q + W = (50 300 3 100) J [as T
f
= 2 300 K = 600 K]
= 14.7 kJ
AH = 14700 + 10 100 = 15700 J = 15.7 kJ.
14. (+ ni n (+ nii + ~i<zi n = 1 atm + l-- it <i + lz =n-ii = =il- ti -i t :=+i
il-i+ ~i-- 1L = -= ~-ii -+ c-i t ti ~l--n <i. ir <i + i ti i-i t l< n = +i
il-i+ -ini- 300 K t -i := +n n l-+i +i +n (-i i l- - +i ni- l--- ti ni
[R = 0.082 L atm mol
1
K
1
= 8.3 J mol
1
K
1
].
(A) 0 (B) Rn (24.6) (C) R n (2490) (D)
2
3
Rn (24.6)
Sol. (B) AS = nR n
|
|
.
|
\
|
i
f
V
V
= Rn
|
|
.
|
\
|
f
i
P
P
= R n |
|
.
|
\
|
atm 1 L 1
R 300
= Rn (24.6)
15. (+ ~i<zi l+-ni ai = + ln( C
p.m.
= aT
3
, ti a l--i + t l< 10K C
p.m.
+i ni- 0.42 J/Kmol t . -i 10K
ni n (- i i l--- t
(A) 0.42 J/K-mol (B) 0.14 J/K-mol (C) 4.2 J/K-mol (D) zero
Sol. (B) 0.42 = a(10)
3
a = 0.42 10
3
S
m
= }
10
0
. m . p
T
C
dT =
mol K / J 14 . 0
3
42 . 0
] 0 10 [
3
a
aT
10
0
3 2
= = =
}
16. l---lnli- l<( n( ~i +i =
<ii AH (kJ/mol) S(J/mol K) AG (kJ/mol)
FeO(s) 266.3 57.49 245.12
C (n+i:) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) 110.5 197.6 137.15
t -i ai- +il( l= l--- ~lil+i -- ti -i t
FeO(s) + C (n+i:) Fe(s) + CO(g)
(A) 298 K (B) 668 K (C) 966 K
(D) AG i-in+ t ~- ~lil+i +ii ii -- -ti ti ni
43
CHEMISTRY
Sol. (C) FeO (s) + C (n+i:) Fe (s) + CO (g)
(1) AH = 0 + [ 110.5] ( 266.3)
= 110.5 + 266.3 = + 155.8 kJ/mole
(2) AS = 27.28 + 197.6 57.49 5.74
= 161.65 J/mole
(3) AG = AH TAS = 0
= 155.8 T 161.65 10
3
T 161.65 10
3
= 155.8 ; T = 963.8
17. l<Ag
+
(~--- ---i), NO
3
(~--- ---i), Cl (~--- ---i) ~i AgCl
(s)
+ ln( AH
f
+nzi 105.579, 207.36,
167.159 -ii 127.068 t - ~lil+i + ln( (-i-i l-- +i ni-i +i
AgNO
3(aq.)
+ HCl
(aq.)
AgCl
(s)
+ HNO
3
(aq.)
(A) 21.471 KJ/mol (B) 145.688 KJ/mol (C) 65.488 KJ/mol (D) +i: -ti
Sol. (C)
AH
reaction
= [AH
f
(AgCl) + AH
f
(H
+
) + AH
f
(NO
3
)]
[AH
f
(Ag
+
)] + AH
f
(NO
3
) + AH
f
(Cl) + AH
f
(H
+
)]
= 127.068 [105.579 167.159]
= 65.488 KJ / mol.
18. 25 g n +i 1 i nni l-- ir <i + lz373 K il- l+i i-i t -i i nni + lz l+
n +i +i ni-i +i ( =i ni-i ni l+ i i = n = l-ni +i in- +-i t l<i ni t i- +i ni n
(-i-i 9.72 kcal/mole t -i+- +n n ~i--l+ -i +i l-- +i t
(A) 1294.0 cals, 11247 cals (B) 921.4 cals, 11074 cals
(C) 1029.4 cals, 12470.6 cals (D) 1129.3 cals, 10207 cals
Sol. (C) Mole of H
2
O= 1.39
Pv = nRT
1 v = 1.39 0.082 373
v = 42.80.
w = Pext. dv
= 1 [42.80] atm lit.
= 42.80 101.325 J
=
2 . 4
325 . 101 80 . 42
cal
= 1024.8 cal.
AH = AE + [PAv]. = 12470.6 cal/s.
19. l--- =ni+i + ln(
C(tii)+ 2H
2
(g) CH
4
(g) AH
1
C(g) + 4H(g) CH
4
(g) AH
2
-i: l+
(A) AH
1
= AH
2
(B) AH
1
> AH
2
(C) AH
1
< AH
2
(D) AH
1
= AH
2
+ A
vap
H(C) + A
diss
H(H
2
)
Ans. (B)

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n =i ~i- + lni+- +i (-ini +i := v+i = v<lzi- +- t

+ =ii lnn+ ~li l-

,aq) = { 286.1 ( 57.1)} kJ mol

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