Physical Chem: Notes Set 2

8/12/2019 Physical Chem: Notes Set 2

1/30

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2/30

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3/30

70#0" 89&:0%+&;

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+,-A

S

V

))# " #,",+ 3>*-,)/* )3);V? );S? R -/*#,"*,' 3/0 "%% 9",.# S VA

Work and heat are not state functions but path functions

The change in the state function is independent of the path taken.


4/30

=!7


5/30

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XOFVS[X8 W0/-+##7 S -/*#,"*, 90+##>0+ 90/-+##A

XOF8YF[X8 W0/-+##7 S -/*#,"*, N/%>L+ 90/-+##A

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#1#,+LA

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;J.+ #1#,+L %/#+# +*+0!1A?

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#>00/>*2)*!#A ;J.+ #1#,+L !")*# +*+0!1A?


6/30

A6B C"*+0D @#E #&$ 8%*/0 @#E

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FD" G"*+0D -#E $"H%&"/ 0D" 0".)"*#09*"6

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C"*+0D @#E +H FD"*.+$O.%:/;


7/30

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X* 8.+L @aQ7 "#


8/30

Z*+0!1 -"* 5+ +6-."*!+2 5+,&++* " :-+/"$ /O/0"."*2

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P"#0 $;

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7e a7 X3 ,.+ #1#,+L 0+%+"#+# .+", ,/ ,.+ #>00/>*2)*!#

;+6/,.+0L)-?


9/30

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3%/ 30/L " ./, #>5#,"*-+ ,/ " -//%+0 /*+A

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;:fgM:hH@?

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10/30

Q+*R %;

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Z69"*#)/* 4/0(7

%J &'( )

)*3)*),+#)L"%

48R ^'

X, -/#,# +*+0!1 ,/ &/0(i


11/30

D/0 " :-+/"$ /O/0".' ,.+ 3)0#, %"& -"* 5+ +690+##+2 "#7

wqUUU initialfinal dwdqdU )*3)*),+#)L"%7

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;4")# ,.+ )*3)*),+#)L"% -."*!+ )* )*,+0*"% +*+0!1?


12/30

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/3 "* )2+"% !"#A

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;30++ +69"*#)/*?A


13/30

3#-:9-#0%+& +H =5)#&/%+& Q+*R;

final

initial

)( dVpw exX* !+*+0"%7 48R ^'

7 +6,+0*"% 90+##>0+ +6+0,+2 /* ,.+ !"#'

4TF,.+ )*,+0*"% !"# 90+##>0+ ;&?i

O/L+ Z6"L9%+#7

qUwpex 00"? D0++ Z69"*#)/*7

Has nothing to do with path

Path dependent


14/30

initialfinalfinal

initial

VVpdVpw ex

V

V

ex 5? Z69"*#)/* ;8/L90+##)/*? &),.

-/*#,"*, "50"*-90+##>0+7

;",L?

' ;K?

B

:a Ba

J.+ !0+1 "0+" -/00+#9/*2# ,/ ,.+ &/0(

+6-."*!+2A

';K?

Z6"L9%+7 8/L90+##)/* ", B ",L 30/L

')*),"%; Ba K'3)*"%; :a K

initialfinal VVpw ex J12160L40L10atm4


15/30

-? [+N+0#)5%+ X#/,.+0L"% Z69"*#)/*

;8/L90+##)/*? /3 "*


16/30

U"#/9*"."&0 #&$ 3#-:9-#0%+& +H P"#0;

8"%/0)L+,017 ,.+ L+"#>0+L+*, /3 .+",

7R >(' &.+0+ >)# ,.+ .+", -"9"-),1 /3 ,.+-"%/0)L+,+0A

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&.+,.+0 ,.+ N/%>L+ /0 ,.+ 90+##>0+ )# (+9,-/*#,"*,A

J.+0L/L+,+0

O,)00+0

8"%/0)L+,+0


17/30

O9+-)3)- ;>&?1? "*2 E/%"0 Y+", 8"9"-),)+# ;>&?5R >&_6? ",

-/*#,"*, 90+##>0+ /3 #/L+ -/LL/* L",+0)"%#

E",+0)"%

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>&?1' )* ^ k: !:

E/%"0 .+", -"9"-),1

>&?5' )* ^ k: L/%:

S)0 :Aa: II

V+*l+*+ :AaQ :HM

V0"## aAHf II

8/99+0 aAHh HH

Z,."*/% @AB@ :::

m%"## ;W10+6? aAfh II

m0"*),+ aAha II

W/%1+,.1%+*+ @AH II

O,")*%+## #,++% aAQ: II

4",+07 #/%)2 @AaH Hf

K)=>)2 BA:hB fQ


18/30

J.+ ,&/ -"#+#7

#2 3+&/0#&0 >+-9." X*+:"//Y )J :+&/0#&0;

')# -/*#,"*,' "R 7' ;4"R 47'?-%/#+2' 0)!)2 0+"-,)/* N+##+% 5+-">#+ ,.+0+ )# */ 83@Ai

mV

constnconstV

VV Cn

dT

dqC ,

\+3)*),)/* /3 Y+", -"9"-),1 ",

-/*#,"*, N/%>L+7

Y+", -"9"-),1b^_kc

E/%"0 Y+", 8"9"-),1b^_;knL/%?c

2

1

,

T

T

mVv dTCnqU

dTCndqdU

dT

dU

dT

dqCn mVv

nVnV

vmV ,

,,

,

X, ./%2# ;3/0 ) - :+&/06"*2/J :+&/06?7 vqU

"#--+E/ 9/ 0+ R"") 0*#:R +H D"#0 "5:D#&'" #0 :+&/0#&0 W+-9."SS

v

qU


19/30

,2 3+&/0#&0 X*"//9*" X*+:"//Z ["H%&%0%+& +H =&0D#-)O;

J.+ /0#0" H9&:0%+&,.", "%%/& ># ,/ (++9 ,0"-( /3 .+", +6-."*!+ ",

-/*#,"*, 90+##>0+ )# -"%%+2 =&0D#-)O0A X, )# 2+3)*+2 "#7

0 "\&)Z*,."%917 bBc R b^c

E/%"0 Z*,."%917B5RB_6` bB5c R b^_L/%c

, :+&/06& ;/3 ,.+ )*,+0*"% 90+##>0+ /3 ,.+ #1#,+L?7

pp qVpVpqVpUpVVpUH )()(

P"#0 *"-"#/"$ +* #,/+*,"$ ,O # /O/0". #0 :+&/0#&0 )*"//9*" %/

"]9#- 0+ 0D" :D#&'" %& "&0D#-)OS

The relationships between U and qv and between H and qp are the same.


20/30

\+3)*),)/* /3 Y+", -"9"-),1 ",

-/*#,"*, 90+##>0+7

Y+", -"9"-),1

b^_kc

E/%"0 Y+", 8"9"-),1

b^_;knL/%?c

mp

constnconstp

p

p CndT

dqC ,

2

1

,

T

T

mpp dTCnqH

dTCndqdHdT

dH

dT

dqCn mpp

npnp

p

mp ,

,,

,

X, ./%2# ;3/0&J :+&/06"*2/J :+&/062; pq

0#--+E/ 9/ 0+ R"") 0*#:R +H D"#0 "5:D#&'" #0 :+&/0#&0 )*"//9*"SS

pqH


21/30

[+%",)/*#.)9 5+,&++* >'?5"*2 >&?53/0 "* )2+"% !"#7

4B5; 4"5C D4( 4B ; 4" C 6D4(B ; " C &' ; " C 6D(

RCRdT

dU

dT

RdTdU

dT

dHC mV

mmmmp

,,

RCC mVmp ,, Z6"L9%+7

E/*/",/L)- )2+"% !"# ;#$%$' Y+%)>L?7

RCRC mpmV2

5

2

3,,


22/30

Z6"L9%+7

J&/ L/%+# )2+"% !"# ;>'?5R H[_@? )*),)"%%1 ", a "8 "*2 @ ",L >*2+0&+*, " 3>%%

+69"*#)/* "!")*#, " -/*#,"*, +6,+0*"% 90+##>0+ /3 : ",L' "*2 2)2 @ (^ /3 &/0(A

8"%->%",+ "' B' "*2 73/0 ,.+ 90/-+##A

At the end, the two pressures will be equal


23/30

Z6"L9%+7

J&/ L/%+# )2+"% !"# ;>'?5R H[_@? )*),)"%%1 ", a "8 "*2 @ ",L >*2+0&+*, " 3>%%

+69"*#)/* "!")*#, " -/*#,"*, +6,+0*"% 90+##>0+ /3 : ",L' "*2 2)2 @ (^ /3 &/0(A

8"%->%",+ "' B' "*2 73/0 ,.+ 90/-+##A

& ) ! / &'(

%&%0%#- @ ",L o a "8 @ L/% : ",L

H%- : ",L o o @ L/% : ",L

i

iiiii

pnRTVnRTVp

wVpVpVVpVVpw ifffiffifex )()(

nR

w

p

pTTw

p

pnRTwVpVpnRT

i

f

if

i

f

iiffff

wqU

TnCqU

TnCqH

nRTpVRCC

mVV

mpp

mVmp

,

,

,,*#@2/.6,+

*/*I)#/E'

&@3F/F,+

*/*I)#/''

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90/-+##iii

wUqTnCqU

TnCqH

nR

w

p

pTTTT

mVV

mpp

i

f

iif ,1

,

,

TnCTRCnTnRHpVHU mVmp ,, )()(


24/30

Z6"L9%+7

J&/ L/%+# )2+"% !"# ;>'?5R H[_@? )*),)"%%1 ", a "8 "*2 @ ",L >*2+0&+*, " 3>%%

+69"*#)/* "!")*#, " -/*#,"*, +6,+0*"% 90+##>0+ /3 : ",L' "*2 2)2 @ (^ /3 &/0(A

8"%->%",+ "' B' "*2 73/0 ,.+ 90/-+##A

m)N+* 6R @ L/%' (.R @fHA:Q k' &.R @ ",L' 8R @ (^' R&G R : ",L

'.R 6D(._&. R @ L/% hAH:B ^ k: L/%: @fHA:Q k _ @a@MQa W" R aAa@@B:@f LH

8R'R

:a:H@Q W" ;'G

'. ? R

@aaa ^

'G R ;@aaa ^ _ :a:H@Q W"? p aAa@@B:@f LH R aAaB@:Q:@ LH

(GR&G'G_6DR @QMAhQB k

J5.406)(23,

ifmV TTRnTnCU

J4.677)(2

5,

ifmp TTRnTnCH J5.1593

)J2000(J5.406

q

q

wUqwqU


25/30

Z6"L9%+7

J&/ L/%+# )2+"% !"# ;>'?5R H[_@? )*),)"%%1 ", a "8 "*2 @ ",L >*2+0&+*, " 3>%%

+69"*#)/* "!")*#, " -/*#,"*, +6,+0*"% 90+##>0+ /3 : ",L' "*2 2)2 @ (^ /3 &/0(A

8"%->%",+ "' B' "*2 73/0 ,.+ 90/-+##A

m)N+* 6R @ L/%' (.R @fHA:Q k' &.R @ ",L' 8R @ (^' R&G R : ",L

'.R 6D(._&. R @ L/% aAah@aM K ",L k: L/%: @fHA:Q k _ @ ",L R @@AB:Bf K

8R'R

:a:H@Q W" ;'G

'. ? R

@aaa ^

'G R ;@aaa ^ _ :a:AH@Q (W"? p @@AB:Bf K R B@A:QH@ K

(GR&G'G_6DR B@A:QH@ _ ;@aAah@aM? R @QMAhB k

J7.406)(23,

ifmV TTRnTnCU

J9.677)(2

5,

ifmp TTRnTnCH J3.1593

)J2000(J7.406

q

q

wUqwqU

! % = D - 0


26/30

!"#:0%+& =&0D#-)O; 10

Z6"L9%+ 0+"-,)/*7 Y@F Yp;/7? p FY;/7?

"3,+0 0+"-,)/* 5+3/0+ 0+"-,)/*

H2O (aq)

(aq)H

+

OH-

T = 298 K ; p = 1.013 bar

Na+

Cl-

(aq)

(aq)Q

(aq)(aq) Cl

-Na+

T = 298 K (= const.)

pr qHHH reactionbeforereactionafter

j

jmj

i

imir HHH )(reactants(products) ,,

>*(*/&* o ` -/*2),)/*# &q (-"* 5+ 2)33+0+*,

. r7"5#/%>,+ N"%>+ /3#,/)-.)/L+,0)- -/+33)-)+*,#

bL/%c

7 $ $ = D - H ! % I


27/30

70#&$#*$=&0D#-)O +H !"#:0%+& 10I;

j

jmfj

i

imfir HHH )(reactants(products)0

,

0

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0

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))(OHM1())(HM1()OHmol1( 00200 aqHaqHHH fffr

0))(H(

0)),(C(,0))(Cl(,0))(H(

0

02

02

0

aqH

graphitesHgHgH

mf

mfmfmf

J.+ /0#&$#*$ "&0D#-)O +H H+*.#0%+&' GB5?Ha' /3 " #>5#,"*-+H)# ,.+ #,"*2"02

+*,."%91 3/0 ),# 3/0L",)/* 30/L ),# +%+L+*,# )* ,.+)0 #,"*2"02 #,",+ ;#++ 8."*!#HAM? ", " !)N+* ,+L9+0",>0+ "*2 : ",L 90+##>0+A J.+#+ N"%>+# "0+ ,"5>%",+2A

FD" /0#&$#*$ "&0D#-)O +H H+*.#0%+& +H #& "-"."&0 %/ G"*+51 2+3)*),)/*A

Z6"L9%+7

Z*"5%+ ># ,/ -"%->%",+ #,"*2"02 +*,."%91 /3 0+"-,)/*' #,"*2"02 +*,."%91

/3 N"9/0)l",)/*' #,"*2"02 +*,."%91 /3 3>#)/* ;L+%,)*!?A

Z %


28/30

Z6"L9%+#7

"? 8"%->%",+2 ,.+ #,"*2"02 +*,."%91 /3 0+"-,)/* 3/0 ,.+ 0+"-,)/*7

)(OH4)(CO2)(O3)(OHCH2 2223 lggl

O>5#,"*-+ GB5a b(^_L/%c;30/L ,.+ 2","5"#+?

.

bL/%c

8YHFY ;,? @HhAhM @

F@;%? I6II H

8F@;%? HgHAQ: @

Y@F ;,? @hQAhH B

kJ1452.62

kJ)86238(2kJ)(0.003kJ)393.51(2kJ)285.83(4

)(reactants(products) 0 ,0 ,0

.

HHHj

jmfj

i

imfir


29/30

5? 8"%->%",+2 ,.+ #,"*2"02 +*,."%91 /3 N"9/0)l",)/* 3/0 &",+0 ;B .+-?7

)(OH)(OH 22 gl

O>5#,"*-+ GB5a b(^_L/%c;30/L ,.+ 2","5"#+ ", @gh k?

.

bL/%c

Y@F ;,? @hQAhH :

Y@F ;%? @B:Ah@ :

below)Kirchhoff(seekJ/mol44.66:C100At

K298atkJ/mol44.01kJ/mol)285.83(kJ/mol241.82

)(reactants(products) 0 ,0

,

0

m

m

H

HHH

vap

j

jmf

i

imfvap

-? 8"%->%",+2 ,.+ #,"*2"02 +*,."%91 /3 3>#)/* ;L+%,)*!? 3/0 &",+0 ;B .+-?7

)(OH)(OH 22 ls

C0atkJ/mol01.6 mfusH


30/30

J+L9+0",>0+ 2+9+*2+*-+ /3 ,.+ 0+"-,)/* +*,."%917

N%*:DD+HH^/ -#E

Z6"L9%+7

dTDCCC

TH

dTBCACTH

T

T

mpmp

r

T

T

mpmpr

0

0

)()(

)(

)()()(

,,

0

0

,,

0

A + B C + D

A + B C + D

T = 1000 K

T0= 298 K

)( 00

THr

)(0 THr

[+-"%%70)# " #,",+ 3>*-,)/* @0a;(? R \ \

X* !+*+0"%7

dTCCTHTHT

T i j

jmpjimpirr reactantsproducts)()(

0

,,,,0

00

Physical Chem: Notes Set 2

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