THERMODYNAMICS
CONCEPT In1hennodynamics,inleraclion ween largeensemblesof obj«ll
•n: s1udi<d and ca1<g0<lzcd. Central 10 this an, the coocepls of
MAP system and surroundings. A system iscomposed of panlclcs whose◄
avcrag• mollons define Its propcrti<s. Propcrm, can be combined
locxprossln1<rnalenergyand1httmodynamlc potent!Ills.
!
latc■slve:Thcscclo not ( E.xtemive: These depend
depend upon quantll)• \!upon quanth)• ol mailer.
r; o rtle·s:;.-.,.-t ;;;;·-P-hy-,-ic·;j· of mailer.,.g..T, P. Ileg.. mass,volume,energy, i Zfflltl;-i::;System in·;h ; j·i
:·L---·"'-·•••--
quantiti<S which art used tod,finc p,--,.--....t' -------------- --_, 'i quiJibrium with c.1c:h other
, thesystem. ................................ J r··..--- ....-
. .-- f ha,'t"same lemperature.
..,.,., .........., ! Elltlwpy(H) ···-·······- ······--·-
Tbtrmodynamlc pro<aHJ I j T01alheatofthei)'Slem ! Finl law, The total enngy of the
Ifdq= 0,proc,.,is adlaballc. I
, • lt=U+PV I univr:rvrtmainsconstant although
IfdT=0and,IE O.theprocess 'i • l1H=!J.U+PlJ.V=Cp/J.1" I ll mi)' undergo runsformal ion
i =lJ.U+ lJ.11.,RT<•t conslont prcssurt) jfmmoocformtothcoth..-.
isisothermii.
IfdV =O,processblsochorlc. i. Ml= }:;H,..uJ.x, - lH, ,,.., j lJ.U=q+w.(.A..,..,_
U
. = lntenulenergy)··••·•·••··
IfdP=O,proc...,isisobnr I =..ve(u01hcrmlc) ,,
l
,1••···-·······...-,.-- ...•
Hal (q) and1,,..capacity(C)
.. ·=ibb=<F=re=eE=lle-rg-y=-=-=-!,
=-I!=-=G=+vc(cndolhcrrnic) (G)
Se-cond law: In a spontaneous
process10101energy of th, univcnc
1ncrc.....
j • lintcapacity,C = ,1,,1dT ! Useful workcloncbythesyst,ni 1 1, t,,S,.,..,,.• AS.,,.m,+AS_,...i,,g>0 I
--------·--·--'- •
lLC •
=(i)U) ·C
iJT I'., ilT ,
• • When n1 moles of gas A ond t12
=(i/H) l•G=lt-TS
'• tJ.G•tJ.H.. rt.S
(Gibb•· Htlmhoh•oquation)
i
_I,
_. ................
Entropy(S)
molesolgasBart mixed.
Mea"""'of mndomn.,., 0< di<ordor
t, \ _ ,l(i'l•L ,w,1,hwu-rc.;,n- 1•.ncl
\ c ,, .,....-n1-C.'1-+-n2'C-,-1 • tJ.S = q :;"
(rcver>lble proces.s)
• t"p.. c• =nR
..........
"1+nl
, ................... ,. ···-'
'
• AG"c -2.JOlRTlogK...,.
• If!J.G=+•·r(Non••pontanrous) j • tlS =2.JOJ11C,log(;,)
r:··:-... fiirk(.., ............ I If!J.G=-vo(Spontanrous)
Entul:py or combaslioa, !J.)I
-··--•·••···
+l.)Oln/1tc>g() I
j
limwnlbl• lsothennal cxpan,lonlj , It is the enthalpy change,.,t,cn I mole I. M= l.JOJnCr tog[!.I.J I
(•II=
[ • II=
' -2.l.0311RTlog(/'1/ Pi) • L·--- 1 subsumc - rnlcompletelyinllir.
-
..................- .. ..·-·-·············· i
' -2..l03nRTlog(l'1 I V1)
I u...•,law of•-•• beat +l.JOJ, :108' !1 JI:
! I rcvorsiblcisolhtrrnal cxpalUionII P
aummatlo•
)l • l
trR ! :
• 11'=11• CdTy=--1 (T,..-7:,) jtl/-l=MI, +ll/l1+/1H3
I • M= l..l0311Rlog(
[reversible adiobatic,xpansion) ---··-················-····-··-··--· · .· ·., ''..,..... ! I l""IO<m>Olj
whcrt,Y• c,,1c,, 1• M =Ll03nRlot{ !1) i
• IV=-P.._.,R('t;-PT
, ,P,)
; P1P! f,
• <1S = l.30lr,CPlo,gl -) !Isobaric] J'
j (irrovcrsiblc adi•baticexpansion)
j I ---·-··...
i
r- .........-.-
Boed mlhalpy
·-·7
............
Eotlwpyol fonnation
i It i• the enthalpy change occurring
1
jTllirdlaw
·-·········••"''''····- ················ "·
1
during the f0<m•1lon of I mole of 1
i It Is lhc enthalpy change i 1 1 • Entropy of all pure cryslols Is icro
i accompanying th, breaking of one i
i iubstanufromitsclcmcnts. l IIthcabsolu1eierotempemurc.
moleofcovaknt bonds. ; i• lim$e0
! J i-0
Bondcnlhalpy= i
L
ll<JnJ rnth,lpi<• of r<.Clllnb I 1
• Rniduol Entropy
1, S•=klnlV
-LBond l'nlhillpiesof proJum! ! (IV=thmnoclynamic probability)
CONCEPT In1hennodynamics,inleraclion ween largeensemblesof obj«ll
•n: s1udi<d and ca1<g0<lzcd. Central 10 this an, the coocepls of
MAP system and surroundings. A system iscomposed of panlclcs whose◄
avcrag• mollons define Its propcrti<s. Propcrm, can be combined
locxprossln1<rnalenergyand1httmodynamlc potent!Ills.
!
latc■slve:Thcscclo not ( E.xtemive: These depend
depend upon quantll)• \!upon quanth)• ol mailer.
r; o rtle·s:;.-.,.-t ;;;;·-P-hy-,-ic·;j· of mailer.,.g..T, P. Ileg.. mass,volume,energy, i Zfflltl;-i::;System in·;h ; j·i
:·L---·"'-·•••--
quantiti<S which art used tod,finc p,--,.--....t' -------------- --_, 'i quiJibrium with c.1c:h other
, thesystem. ................................ J r··..--- ....-
. .-- f ha,'t"same lemperature.
..,.,., .........., ! Elltlwpy(H) ···-·······- ······--·-
Tbtrmodynamlc pro<aHJ I j T01alheatofthei)'Slem ! Finl law, The total enngy of the
Ifdq= 0,proc,.,is adlaballc. I
, • lt=U+PV I univr:rvrtmainsconstant although
IfdT=0and,IE O.theprocess 'i • l1H=!J.U+PlJ.V=Cp/J.1" I ll mi)' undergo runsformal ion
i =lJ.U+ lJ.11.,RT<•t conslont prcssurt) jfmmoocformtothcoth..-.
isisothermii.
IfdV =O,processblsochorlc. i. Ml= }:;H,..uJ.x, - lH, ,,.., j lJ.U=q+w.(.A..,..,_
U
. = lntenulenergy)··••·•·••··
IfdP=O,proc...,isisobnr I =..ve(u01hcrmlc) ,,
l
,1••···-·······...-,.-- ...•
Hal (q) and1,,..capacity(C)
.. ·=ibb=<F=re=eE=lle-rg-y=-=-=-!,
=-I!=-=G=+vc(cndolhcrrnic) (G)
Se-cond law: In a spontaneous
process10101energy of th, univcnc
1ncrc.....
j • lintcapacity,C = ,1,,1dT ! Useful workcloncbythesyst,ni 1 1, t,,S,.,..,,.• AS.,,.m,+AS_,...i,,g>0 I
--------·--·--'- •
lLC •
=(i)U) ·C
iJT I'., ilT ,
• • When n1 moles of gas A ond t12
=(i/H) l•G=lt-TS
'• tJ.G•tJ.H.. rt.S
(Gibb•· Htlmhoh•oquation)
i
_I,
_. ................
Entropy(S)
molesolgasBart mixed.
Mea"""'of mndomn.,., 0< di<ordor
t, \ _ ,l(i'l•L ,w,1,hwu-rc.;,n- 1•.ncl
\ c ,, .,....-n1-C.'1-+-n2'C-,-1 • tJ.S = q :;"
(rcver>lble proces.s)
• t"p.. c• =nR
..........
"1+nl
, ................... ,. ···-'
'
• AG"c -2.JOlRTlogK...,.
• If!J.G=+•·r(Non••pontanrous) j • tlS =2.JOJ11C,log(;,)
r:··:-... fiirk(.., ............ I If!J.G=-vo(Spontanrous)
Entul:py or combaslioa, !J.)I
-··--•·••···
+l.)Oln/1tc>g() I
j
limwnlbl• lsothennal cxpan,lonlj , It is the enthalpy change,.,t,cn I mole I. M= l.JOJnCr tog[!.I.J I
(•II=
[ • II=
' -2.l.0311RTlog(/'1/ Pi) • L·--- 1 subsumc - rnlcompletelyinllir.
-
..................- .. ..·-·-·············· i
' -2..l03nRTlog(l'1 I V1)
I u...•,law of•-•• beat +l.JOJ, :108' !1 JI:
! I rcvorsiblcisolhtrrnal cxpalUionII P
aummatlo•
)l • l
trR ! :
• 11'=11• CdTy=--1 (T,..-7:,) jtl/-l=MI, +ll/l1+/1H3
I • M= l..l0311Rlog(
[reversible adiobatic,xpansion) ---··-················-····-··-··--· · .· ·., ''..,..... ! I l""IO<m>Olj
whcrt,Y• c,,1c,, 1• M =Ll03nRlot{ !1) i
• IV=-P.._.,R('t;-PT
, ,P,)
; P1P! f,
• <1S = l.30lr,CPlo,gl -) !Isobaric] J'
j (irrovcrsiblc adi•baticexpansion)
j I ---·-··...
i
r- .........-.-
Boed mlhalpy
·-·7
............
Eotlwpyol fonnation
i It i• the enthalpy change occurring
1
jTllirdlaw
·-·········••"''''····- ················ "·
1
during the f0<m•1lon of I mole of 1
i It Is lhc enthalpy change i 1 1 • Entropy of all pure cryslols Is icro
i accompanying th, breaking of one i
i iubstanufromitsclcmcnts. l IIthcabsolu1eierotempemurc.
moleofcovaknt bonds. ; i• lim$e0
! J i-0
Bondcnlhalpy= i
L
ll<JnJ rnth,lpi<• of r<.Clllnb I 1
• Rniduol Entropy
1, S•=klnlV
-LBond l'nlhillpiesof proJum! ! (IV=thmnoclynamic probability)
