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4.7.2 First low of ther1nodynomics for
•
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i. lsothermol process : Temperature is constant
in such process, internal energy is constant.
Hence, !),.U.= 0
For isothermal process
0 = Q + W or W = -Q .......(4.1 4)
The above equation implies that heat
absorbed by the system is entirely used for
doing work on the surroundings. When work
is done on the system by the surroundings it
results in release of heat.
ii. Adiabatic process : In adiabatic process,
there is no exchange of heat between system
and its surroundings that is, Q = 0. then
-11U=-W ....... (4.15)
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is done by the system on the surroundings at
the expense of its internal energy, the internal
energy accompanying the adiabatic process
would decrease.
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· •• s
'" P• ocrss · •
. . u t1st1lul1ono f
, From Eq . ( 4 - 19) , d
IJ ·
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/\ s the react,· · · iVI = U2 + P 2V2-
, . on ts corn ed out in a closed
l.: Ont o1ncr v0 I
, •
-
unic ot the system is constan t or
= (U2 - V) + (
,\ t O tlnd = b,.U + b(P V)
ressure,
pi ==
,...... (4 . 17) ..
For con stant p V
. Equation ( 4.17) shows a change in Ml = bV + pt:.
1
n1 crnal e nergy of th e systen1 is due to heat . i·deand c
Ure 1ns ives
trans for at const a nt vo lume. The subscript 'V' If the press
= p , Eq. ( 4 . l 8) 9
ind ica tes that heat is transferred at the constant p exl u+ p ~v
vo lutnc. Furth er U be ing a state function, Q" is Qp = D.
a lso a state function . . (4 22) a n •
From equation s .
iv. Isobaric process : Usually chemical ~ = Qp
react io ns arc carried out in the open container s
under constant atmospher ic pressure. ln such Th us change in de r1
.
reactions, ~ V -:t- 0 e ual to heat transferr e
q
pressure. H an d QP are stc
Replacing Q by Q,, and ~u by Qp - P e rl ~ v in
equa tion ( 4.16) gives 4 .8.1 Relation ship bet'"
chemica l reaction s : A t '
Q" = ~u + P,.\, ~v ... .... (4.18)
and ~U are related as
The reactions carried out in open
containers under constant atmosphe ric Af-1 = ~U+ P~V
pressure are common in che1nistry~ a ~pecial i. For reaction s involvin g
syn1bo l ~ fl , the enthalpy change, 1s given to usually is very small (sc
indi cate heat changes occurring at constant show volume change wi·
pressu re.
and Aff = ~U
Remember... ii. For reaction s involvin
not a state function.
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c,j- (. 0 Yl S +a \JJ · D l 1'_ ! ~ U. Tt' ·

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Y:2.0 "> -~➔ H 2 O fr) ~(onH.

A :: -40
r
 II
Re.\Q..-1-;-0>"l sh;p be.-huten ~H anol... A\D. -fc.!
C n~ p-,'i c cJ -er- e. o. c..h' o "'-

A- -\- Con~ +-a ~t pir-~ .tsu Ye A H = .A \.J + P 6. V

\> 'F-o lr .coli d anol ~ a..sl ~ ha 'I is

-is- e ac.. h' ol" .s. ~
0

y
b.H ~4U t- PAV
C
:=:: Au +- p CV 2.. - \I,)
~ ~u +- P/ 1.-'P t 1 - - <D
\/ , a d v J.. l ~ ~ t2.T
"o u'"' e of ..9 cu f h [Link]. of re.o.d-o. ~
(l.. T 'n 1
""

o-nd J:' ..- f~ p e.c.+;vvj

, [Link]
~U"Plill\j ..- [Link]-.. t OY\J p-ro cl~c..t- [Link].l id e....l\j.
App lji~j 1ol ~J _9a..s. eyu~h'o"'- P'I/::;, l"I R..T
_,. "Y\1 m o \ .e..s ~~
u c.e
'"'n, mo .e _p.-o_d_
"lr e o c...+ uJ-
' -..-1!. ll• p,, o c:l. u d-

-rll e i ol eoJ j ns ~ 7u. cd> "OIA.. 3 i lfe

pv I ::. 1"11 R.i anol p v.... = nl.- ~T - - ©
L:::. µ + 1"h-~T- ri, R. T
:= bLJ
:::. fl U + (ii i - n ,) 52..T
-----
v\--1 ::= b. V + Li ~ F•-T- ,j
Lv h"' T-e. .b nj i..s. cL'f ~b eI'\(e b ~h'-' e -e. I'\ ,,, u w-. b~.7f o f-
llf'l o I".s of ptr o d u c.:1-.s an d ~ 0..t-e o f- b e Qt . r,. f
 En -11-o.../ P"J ~f [Link] i rria.:h·ol'J ( 6 .sub H )
SY1 -11-tc...l P.'.f d, c, n j€ -foY Cc:,n ve -ios' o "1. of o I,\ e
rriole. of- "l<ntl c:u.:t- ~ol,·cl. d.h e [Link] 1"' "fl> [Link]. .,.-
a....t C. O"\"\ t +o J- i~ 1"rt pt~ J--u.,.,. e Q -n of p1r ~ ..1.S. u. r<' . _,
H2-0 C!,) _ _.,., Hl-0(9) ~subH-= S-J · C>i> kJl\'\OI
a.r D6C.

H~ oc~, __., H2..0 C.o.) ~fus'H = c;. oJkT r,,o(

H "l.. O <' i ---" '12.0 (~) _l). v•-p M = '-I,;: · O 7 /c J !

f'l'IO
-
H 1,.(;(n " Hz.. O ('3) ,6 ~ub ~ .::. 'S"' I. () R k T r-,o I
-- - -
ti ~~b-~ -4 f ,.s H -t ./2.v.,_p i:i-1
r-
t= " *. ~-b_j o J ' o n i3 4.:1) 0 111 ,A Io H
En -tti~ P',1 • I" o.l'I j e. 0 cc O '""'P O 'tlj i""j -Ji, ,(, y ~ Mo.,, J ot
av. e -" c.ho1,1.,. · 1r om 011 e m o le of- [Link].s ofo"1
~ -
No -9 ) t\l ~ + e - }j ;or\ ~ .: ~ g I-( t1 "1 o\

J,4-'lttf 1 ../ ~w 'l..u:l . f 0 ~ ) 0 n ;3~·0K.

f j,e c.➔ ~o n 9~ e11 -¾-1~ Pj )

f, l'l ¼ 11.. /Pj cJ, o. 1A.3e i,J h~ ~ OI\ e mol~c,..J..e of a1 '!'~ o .se
cJn w, o. a -e p+ 't!- o n cJ fo .-r111 ~ °' ~ ~ oUJ Cl!"' • () \,(,
A -1
Clt,) f e- __,, er D P3 H::. - 34~ J T o1
_f-n¾-.,/ py of oib)'r) i3cth~o vi ( A oJbm ~l)
f n~a.,Jpj ci\altje. ac cofl'\pcn,~;~!J J..ls.s oc/~~ 0 (?)f- oJte
Mole. of 9 ct! eou..c -' U. b ..J........ _ L o ~l ~
ra t1( ,e •I~ .L.o_ tl.1 ~, 1 ~ ~ 't' ~ '"1 "Jry
1

of cJu m'.~ tLh. o i,_t . , _1

C I -:i-<!-i 1 ~ C I C,l +C1 er, ) ii CJ..h:.lfl H ::: 2 4 ·t J:::T ~
iii. lsochoric process : Substitut ion of
f,rom Eq (4 . I 9), we [Link]
I I, U • P, V und If - l
-
W -f> ' ,1 L\Vi ntol.:.q .(4.12 ) With the.;<,<.:
(4 .16)
t:iU -- Q- p L\V U • PV ~/.., }
PV
I'\ ( j i I

. · 0 cJ01,cd
As the reaction is earned out in (U U/ · (P_V1 - /-' V;
. . ·t . n is constant or
<.:ontam~r, volume of the sys er ·
b.U ,. l\ (PVJ
t\V -- 0 and
...... (4 .17)
r
For constant prcc.,c.;ure, pl p /-' and

Equation (4. I 7) shows a change in !1H = !1U +- P/\ V

interna l energy of the system is due to heat If the pressure insi de and outside is the \orn:
. ' V'
transfer at consta nt volum e. The subscnpt
p = P, Eq. (4 .18) gi ve~
indicates that heat is transferred at th e constant ex/

Q = 1:-.U + P (),f/ (4 .L·

volume . Further U being a state funct ion, Qv is p
also a state fu nction. From equations (4.22) and (4.23)
iv. Isobaric process : Usuall y chemi cal f 4.:,
11H = Qp
reactions are carried out in the open contain ers
under constan t atmospheric pressure. In such Thus change in enthalpy of a ,y'>ter:.
reactions, 11 V -:t= 0 equal to heat transferred from it at the constc~
pressure. H and QPare state functions.
Replacing Q by Qfl and 11U by Qfl - Pex / 11V in
equatio n (4. J 6) gi ves 4.8.1 Relationship between ill onrJ .... ' ,
...... . (4.18) chemical reactions : At constant pressure, J
Q = 11U + P 11V
p ex /
and !1U are related as
The reactions carried out in open
containers under constant atmospheric
pressure are common in chemistry, a specia l i. For reactions invol ving solids and liquids, ~;
symbol 11H, the enthalpy change , is given to usually is very sma ll (solids or liquids do r.r_
indicate heat changes occurring at constant show volume change with change of pres::iur~
pressure. andM = 11U

Remember... ii . For reactions involving gases, .1V cannot:;

q is not a state function. neglected and
Whereas Qv and QP are state Mi = 11U .J... Pl1 V
functions.
= 11H + P(V_, - VI)
4.8 Enthalpy (//) : Enthalpy of a system is 11H = 11U T PV2 - P VI ... (-4.2:
sum of interna l energy of a system and the
where VJ is the volume of gas phase reoctam~
energy equivalent to PVwork.
and V2 that of the gaseous products.
H = U+ PV .. ..... (4.19)
We assum e reactant and product behm~
Chang e in enthalpy, 11H, is also state ideally. Appl ying ideal gos equation Pr= nRI
function given by When n J moles of gaseous reocta nb produce
11H = I-!2 - HJ .. .. (4.20) 11 2 moles of gaseou s products. The ideal ga~
equation give,
where H J and H2 arc the [Link] of initial
and fin al states, respectively. PV, = nlTan dPV,. = nJ?T
.
... (4Y

72
 ds
s ubst itution of Eq . (4. 26) into Eq. (4.25) yiel Pro blem 4 .9 Calc ulat e the- work don e
in
Mf = !iU + n~T - n,R T oxid atio n_of 4 mol es of s0 2 at 25 oc if
= !iU + (n 2 - n) R T 12 SO/ g) -+ 0/g ) - ---. 2 SO, (g)
= !iU + An RT .. ... .. (4 .27) R = 8.31 4 J K 1mo) 1
I}

of State whe ther wor k is done on the system or

where An9 is di ffere nce betw een the num ber by the syst em.
moles of products and thos e of reac tant s.
~olution :
- !iH for the reac tion ,
v hi rn 4 ....
~or oxid atio n of 4 mol es of SO 2 , the reaction
2C(s) + 3Hi g) - - - C2H/g ) is -84. 4 1S
kl at 25 °C. Cal cula te l:lU for the reac tion 4 SOi(g) + 2 Oig ) - - • 4 SO/ g)
1 1
at 25 °c. (R = 8.31 4 J K· mol · )
W = -6ng RT
0

~(JHH O,l
~n.q = 4 - 6 = - 2 mol, T = 298 K
;).H = l:lU + An fJ RT
Hence,
!!ln = (mo les of prod uct gase s) - (mo les
of
n W = -2 mol x -8.3 14 J K·1 moI ·1 x 298 K
reactant gase s)
- 3 = -2 mo]
= 4955 J = 4.955 J
!::,.n
n
=l J
1 Work is don e on the system (sin ce W> 0).
Ml = -84.4 kl, R = 8.31 4 J K· mo] ·
1

= 8.314 x 10·3 kJ K· 1 mo] · 1 4.8.2 Work done in chemical reaction :

The wor k don e by a syst em at con stan t
Substitution of thes e in abo ve
tem pera ture and pres sure is give n by
-84.4 kJ = AU + 8.3 14 x I 0·1 kJ K· 1 mol ·1 x W = P ex, AV. Assuming P ext = P,
298 K x (-2 mol ) W = - P;).V
= AU - 4.96 kJ
= - P (V2 - V)
Hence, AU = -84. 4 kJ + 4.96 kJ = - 79.4 4 kJ 1
= - PV2 + PV I
H the gases wer e idea l, using Eq. (4.26)
1
_ . __ __ _)
Under what conditions ll.H_-_ A_U? PV, = nlT and PV2 = nfiT
At con stan t tem pera ture and pres sure .
In o particular reaction 2 kJ
•• 1
W = - njl. T + nl T
of heat is released by the system and 6 kJ
of work is done on the system. Determine
= - (n2 - n) RT
' of 11.H and tiU? ···· ··· (4.2 8)

""·,I '•c 1 Acc ord ing to the first low of The abo ve equation give s the wor k done by
the system in chemical reac tions. The sign
of
thennodynam ics
W dep ends on ~ V. We consider the following
tJ. U =- Q + f,y
cas es:
Q = -2 kJ, W = +6k J If n i > n I' ~ n 11 is pos itive a nd W < 0
l. .

AU :::: -2 kJ + 6 k.T == + 4 kJ or work is done by the system.

ii . If n 1> n 2• ~ n[J is neg ati ve and W> O
· Q,, -== Mi == - 2k1
or work is done on the system.