0,STG

-

-

-

-

21

2

1

2

2rmD

2

2rd

22rhht

Sd

Sc HH

chc

chdup HHH .

TQ

TT

QC

12

T = 110-50 = 60C (60K)

: 233 x 103 mol (55,8g/mol) = 13,0.106 g (13,000 kg)

= T

= 0,45 J g-1 K-1 13,0 x 106 g 60K

= 351.106 J

T

QEntropyS

TQS TN

T

QdS TN

T

QS TN

T

QS BTN

-

T

Qds TN

2

1

T

T T

dTCS

CdTQTN

T

dTCS

T

T

P

2

1

TdTCS

T

T

V

2

1

T

QQ

TT

QS TT

1

T

HS TT

1

2lnV

VnRTQT

2

1

1

2 lnlnP

PnR

V

VnR

T

QS T

00TS

T

dTnCSSSS

T

T

TTTT

0

0

HHLLRR SSSSS 54321

543210 SSSSSSSSS TTT

0TS0

298S

S

PUSP SSS

)()( 02980

298

0

298 tgSspSS

0S

S

)()(2

1)( 322 kSOkOkSO

081,94)(2

1)()( 12

0

2982

0

2983

0

298

0

298 JKOSSOSSOSS

S

S S S

S S

S S

S S

T

H

T

HS mtmt

00 STHT

HS

0STH

0,STG

0

298G

)()( 02980

298

0

298 tgGspGG

ST

G

ST

G

P

)(

HGT

GT

T

GTHG

P

P

(

)(

22

)(

T

H

T

GT

GT

P

PT

G

T

2T

H

T

G

T P

0

298G )(0 TfHT )(

0 TfGT

2

1

2

1

2

1

12

P

P

TpTp

P

P

T

VdPGG

VdPdG

VP

G

)( 1212 PPVGG TpTp

P

RTV

12ln12 P

PRTGG TpTp

PRTGG TT ln0

( Hf0)

( S0)

C2H5OH(k) + 3O2(k) 2CO2(k) + 3H2O(k)

a) ( H0)

H0 = p Hf0( ) - r Hf

0(

H0 = ((2 (-394)+(3 (-242)) - ((1 (-234)+(3 0)) kJ /mol

H0 = (-1,514) - (-234) kJ/mol

H0 = -1,280 kJ/mol 1,28 x kJ /mol

b) ( S0)

S0 = pS0( ) - rS

0( )

Hf0 (kJ/mol) S0 (J/mol K)

C2H5OH(g) -234 283

CO2(g) -394 214

H2O(g) -242 189

O2(g) 0

S0 = ((2 214)+(3 189)) - ((1 283)+(3 205)) J/mol K

S0 = (995) - (898) J/mol K

S0 = 97 J/mol K 0.097 kJ/mol K

c) G0 298K

G0 = H0 T. S0

G0 = (-1,280 kJ/mol) - (298K)(0,097 kJ/mol K)

G0 = (-1,280 kJ/mol) - (28,9 kJ/mol)

G0 = -1,309 kJ/mol -1.31 x 103 kJ/mol

d) 298K

( G0

iidnSdTVdPdG

'Wdnii

iidn

VPP

G

TT

PRTTT ln0

0

T

PNP ii

)ln(0 PNRT iiTiT

0iidn

)()( sptg ii

)()( sptg ii

32

22

3

HN

NH

PPP

PK

3

2

22

3

HN

NH

CCC

CK

iii PRTT ln)(0

pTT RTGG ln0

bB

aA

dD

pPP

P

0000

BADT badG

cbPT RTG )ln(0

RT

GTcbP

0

)ln(

cbP )(

cb

bB

aA

dD

cbPPPP

PK )(

0

TG

PT KG lg575,40

PPT RTKRTG lnln

P

PT K

RTG ln

PP K

PP K

PP K

cb

bB

aA

dD

CCC

CK

.

i

ii n

nx in

cb

bB

aA

dD

xxx

xK

.

cb

bB

aA

dD

nnn

nK

.

n

cbin

nx

ncP n

PKPKRTKK .).(

n

iii PRT ln0

iii xRT ln*

cbxPxPK )( ,,

cbCOP PK )( 2

)0H

PKRTG ln0

2

00

T

H

T

G

TP

2

0

)(

.576,4

lg

T

H

T

K Cal

P

P

H0H H

2

ln

RT

H

dT

Kd P

HH

ncbnP PKK

n

n

n

2

2

CO

COKC

a) Keq 25C.

b)

c)

d)

G0 = -R.T. ln(Keq )

-32,300 J mol-1 = -(8,31 J mol-1 K-1) (25+273K) ln(Keq)

13,0 = ln(Keq)

Keq = 442 x 103

b) G0 = H0 T. S0

G0 = -92,200 J mol-1 - (273 + 475)K (-201 J mol-1 K-1)

G0 = 58,1 x 103 J mol-1

c) G0 = -R.T.ln(Keq )

58,1 x 103 J mol-1 = -(8,31 J mol-1 K-1) (475+273K) ln(Keq)

-9,35 = ln(Keq)

Keq = 8,70 x 10-5

d) Keq 25C: 442 x 103

Keq 475C: 8,70 x 10-5

hQ

A

h

c

T

T1max

R

TTaq i

)( 0

4aTE

)(

2898)(

0max KTm

vm

tvAV

atvArma )(

btvArmb )*(

bvAravAr )()(

VAr

-

-

-

-

WS

WWSS

m

WWSSm QQ

QCQC

Q

QCQCC

lmgsm

smlmgCm /7,26

/)510(

//)5401020(3

3

KCdt

dC

00

)(C

C

C

dtKC

dC

KtC

CCC

0

0 ln)ln()ln(

KteCC 0

lmgC /5,3106,28

100,13

5

KCVQCSdt

dCV

0dt

dC

KVQ

SC x)(

KVQ

SC

V

KVQ

dt

dC

KVQ

Scy

dt

dC

dt

dy

yV

QK

dt

dy

tVQkeyy )/(0

KVQ

SCy 00

tV

QK

t eKVQ

SC

KVQ

SC 0)(

tV

QK

t eKVQ

SC

KVQ

SC 0)(

C

tV

QK

t eCCCC )(0)()(

3

33)(/117,0

500/4,0/100

/140mmg

mhhm

hmgC

tVQKt eCCC

/

)(0)(

(2

1

A

A

C

C

lkg /1

ppm300001000000

30000

100

3

lNmgNHmgNH

mgN/148

18

144

4

lNmgNOmgNO

mgN/214

62

143

3

%100%21

2

mm

mC

litmolVM

mCM /,

.

1;; 2121

22

21

11 NNnn

nN

nn

nN

molanmM

mCm ,

.

1000.

1

2

VN

mCN

.

1

2

2

1

N

N

C

C

V

V

mlC

VV

NaClN

CAgNO

NaClAgNON

803,0

16,0150

,

.3,3

3

3

31050

CaCOeq

mgCaCO

eqgmoleq

molg/50

/2

/100

lmeqmeqmg

lmg/6,4

.20

/92

l

meq

meq

mg6,450

0G

0T

GHS

iii xRTT ln)(*

0H 0V

1'''

iP

P

t

t

P

P

1)1(1 qqN

NNNq

1

1

q

i

OHAOHHA 32

][

]][[ 3

HA

OHAK a

][

]][[

B

OHBHKb

][

]][[

4

33

NH

OHNHKa

][

]][[

3

4

NH

OHNH

14

3 10]][[. 2OHba KOHOHKK

]][[ 2

3

OHHA

AOHK a

][

]][[

HA

AHK a

][

][lg

HA

ApHpK a

]][[

][

HB

BHKb

pHB

BHpKb

][

][lg

gg

g

Wg

gg nn

n

g

32

32 106,1)(aqCO

COHK

lmolCOH

HCOHK /1047.4

][

]][[ 7*

32

31

lmolHCO

COHK /11108,4

][

]][[

3

2

32

lmolCOH

HCOHK /1047,4

][

]][[ 7*

32

31

][

]][[*

32

1COH

HHK

][

]][[2

3

2

32

HCO

COHK

lmolHCO /1026,4611000

260][ 33

lmolCO /100,5601000

30][ 4

2

3

4

311

2

3

32

100,5

1026,41072,3

][

][][

CO

HCOKH

61

][ 3HCO

lmeqKLDL

Mg

KLDL

Ca/4

][][ 22

lmeqMg

/42,12

][

20

40 2

cationanion

2356

x

AgClTS

33

44)2( 2

2

TSSSSTCaF

SSSA 0

SGA S

SG

S

GS

-

-

-

dC

d

RT

Ca

0dC

d

0dC

d

0dC

d

dC

d

)1ln(0 BCAC

KP

PKaa m1

.

n

iii

iimi

pK

pKaa

1

1

000

0

//1/1

/

pppcppp

pcpvv m

00 /11 ppcpp

cpvv m

RTqqne /)1(

0p

px

xcxx

cxvv m

11

pcv

c

cv

p

pp

p

v

p

mm

10

0

0

mm cv

xc

cvxv

x )1(1

)1(

)()1(

)(0

1xf

xv

xhaypf

ppv

p

NA

Svm

022400

-

-

liRi xkP .

0iR Pk

Rk

iii xPP .

0

)1(0110

11 xPxPPP

0

1P

xPPP 010

1

xP

P

P

PP0

1

0

1

0

1

RTM

mnRTPV

M

m

gg

g

atmamtPg 21,0121,0

h

gg K

P

6

41042,6

1027,3

21,0g

Wg

gg nn

n

6,551042,6 6

g

g

n

n

64108,9

1004,8

79,0g

6,55g

gg n

nn

lmolng /1046,54

34 10281046,5SC

lmg /29,15

6

410233,0

10142,0

00033,0g

Wg

gg nn

nn

6,5510233,0 6

g

g

n

n

lmolng /1013,04

34 10441013,0SC

lmg /57,0

hAdt

dC,

srAhAdt

dC,

)( SCCh

k

h

r

dt

dC

h

kt

CC

CC

S

S exp0

h

kt

h

kt

CC

CC

S

S 2/1

0

0 exp2/

k

ht 69,02/1

kht 69,02/1

ht 5,9144,0

269,02/1

ht 1471034,9

269,032/1

tCv

dt

dCv

dt

dn

dt

dn

dt

dnv CBA

-

-

21 nB

nA CkCdt

dCv

21 nB

nA CkCdt

dCv

110)(

212 vv TT

Ni

321

DBAA CCkC

dt

dCW

kkCv 0

OHIHIOH 22222

HIOH CkCv 2

AA Ck

dt

dCW 1

tkC

C

A

A1

0ln

e

CC AA

0

1

0

0

/ln k

eC

C

A

A

1

1

k

AA C

dt

dCW

11

2/1

693.02ln

kkt

22 AA Ck

dt

dCW

tkCdCA

A

C

C

AA 22

0

/

tkCC AA

2

0

11

AA CCtk

0

2

111

ACkt

02

2/1

1

AA

A Ckdt

dC3

BAA CCk

dt

dC 23

CBAA CCCk

dt

dC3

tkCCA

32

0

22

11

2

0AA

CC

2

03

2/12

3

ACkt

AB Ck

dt

dC1

AC Ck

dt

dC1'

AACB Ckk

dt

dC

dt

dC

dt

dC)'( 11

11'

k

k

dC

dC

B

C

1

1'

k

kCC BC

A

A

C

C

tkk 011 ln

1)'(

tkkBA eCC

)'(

011.

tkkAB eCkk

kC )'(0

11

1 111'

tkkAC eCkk

kC )'(0

11

1 111'

'

BAD CCk

dt

dC2

BAE CCk

dt

dC2'

BABAED CCkk

dt

dC

dt

dC

dt

dC

dt

dC)'22

2

2'

k

k

C

C

D

E

AB

AB

BA CC

CC

CCtkk

0

0

00

22 ln)(

1'

ikk

CA k1

DBA k2

BAB CCk

dt

dC2

BAAA CCkCk

dt

dC21

BB

A dCCk

kdC

1.1

2

1

B

BBAA C

C

k

kCCC

02

100 ln

B

BBBAB

B

C

C

k

kCCCCk

dt

dC

02

1002 ln

CBA kk 11 '

AA Ck

dt

dC1

BAB CkCk

dt

dC11 '

BC Ck

dt

dC1'

tkAA eCC

1.0

tktkAB eeCkk

kC 11 '0

11

1

'

11

'

1

11

10

'

.

'

.'1

11

kk

ek

kk

ekCC

tktk

AC

[A] [B] M s-1

1 3,28 x 10-2 M 8,77 x 10-3M 2,85 x 10-2

2 4,92 x 10-2 M 8,77 x 10-3M 4,28 x 10-2

3 4,92 x 10-2 M 1,32 x 10-2M 6,42 x 10-2

4 3,28 x 10-2 M 1,32 x 10-2M 4,28 x 10-2

= k x [A]m x [B]n,

:

( (k x [A2]m x [B2]

n) / (k x [A1]m x [B1]

n) (4,28 x 10-2 / 2,85 x 10-2) = (4,92 x 10-2M)n / (3,28 x 10-2M)n

1,50 = (1,50)n , n = 1.

:

( ) / ( 2) = (k x [A3]m x [B3]

n) / (k x [A2]m x [B2]

n) (6,42 x 10-2 / 4,28 x 10-2) = (1,32 x 10-2M)m / (8,77 x 10-3M)m

1,50 = (1,50)m , m = 1.

B

(giy)

[M]

ln[A] 1/[A]

0 2,50.100 9,16.10-1 4,00.10-1

1 1,88.100 6,29.10-1 5,33.10-1

2 1,52.100 4,21.10-1 6,56.10-1

3 1,29.100 2,56.10-1 7,74.10-1

4 1,12.100 1,17.10-1 8,89.10-1

5 9,98.10-1 -1,88.10-3 1,00.100

6 8,98.10-1 -1,07.10-1 1,11.100

7 8,18.10-1 -2,01.10-1 1,22.100

8 7,51.10-1 -2,86.10-1 1,33.100

9 6,95.10-1 -3,65.10-1 1,44.100

10 6,46.10-1 -4,37.10-1 1,55.100

1/[A] .

=

= (1,55-0.400)/(10-0)

= 0,115

= 0,115M-1s-1

a. (C)

b. ( C)

c. ( B)

d. ( D)

H2(k) + Br2(k) 2HBr(k)

dt

dCVVrQCQC AAAAi 0

dt

dCr AA

dt

dCk A0

t C

C

A

A

Ai

dCdtk0

0

0

tkCC AAi 00

AA Ckr 1

dt

dCCk AA1

0

0

1

A

Ai

C

C A

At

C

dCdtk

Ai

A

C

Ctk 0ln1

0dt

dCV A

00

VrQCQC AAAi

)(0AAiA

CCV

Qr

0krA

QVkCC AAi 00

Q

V

00kCC AAi

01 AACkr

1

0

0 kC

CC

A

AAi

][

][

AK

Akr

SA

CK

Ckk

S

max

SK

Ckk max

maxkk

-

-

SS K

Ck

CK

Ckk maxmax1

SK

MCkMk max1

CC

Mk 5,2100

500005,01

5,21K

CCCk 11

1C

C

C2005,2

0dt

dC

01 rVQCQC

0max1 CK

CMkVQCQC

S

CK

CMkCC

V

Q

S

max1 )(

C

C

100

05,05000

C

CCC

100

2501

C

CC

100

250

5

200

CCC15,2

C

C40055,2

C

CCC

100

2501

h8,19

1

1 lnC

Ctk

CC

K

CMkMK

S

25100

05,050000max1

2000ln1,025

C

dt

dCr

CC

C

C

CK

CMk

dt

dC

C 100

2500

100

05,050000max

dCC

Cdt

t C

C

A

Ai0

01002500

00

1002500A

Ai

A

Ai

C

C

C

C

dCC

dCt

)(ln1002500 00

AAiA

Ai CCC

Ct

ht 1,0

lmgCA /2001lmgCA /640

hlmgCA 174,0,/4,160

4000ln2,025 0

AC

lmgCA /270

)4000(4000

ln10040000

0

AA

CC

t

lmgCA /32200htlmgCA 12,1/270

khneox

kh

ox

a

a

nF

RTEE ln0

F

RT

kh

ox

a

a

nEE lg

059,00

]lg[2

059,0 20 CuEE

][

][lg059,0

2

30

Fe

FeEE

2

8

40 lg5

059,0

Mn

HMnOEE

22

0 lg2

059,0HPOEE

][

][lg

059,0

1

1

1

0

11 kh

ox

nEE

][

][lg

059,0

2

2

2

0

22 kh

ox

nEE

][

][lg

1

][

][lg

1059,0

1

1

12

2

2

0

1

0

2 kh

ox

nkh

ox

nEEE pin

][

][lg059,077,0

2

3

Fe

FeE

][

]][[lg

5

059,051,1

2

8

4

Mn

HMnOE

][

]][[lg

5

06,051,1

][

][lg06,077,0

2

8

4

2

3

Mn

HMnO

Fe

Fe

852

4

532

][]][[

]][[

HFeMnO

FeMnK

Klg5

56,0

d

Ox

nF

RTEEh

Reln0

22

4

20

][

]][[ln

4 OH

HO

F

RTEEh

4

2 ]][[ln964874

298314,823,1 HO

]lg[2]lg[4]lg[lg][

2

24

2

eHMnKeH

MnK

2

64843

2

4]lg[43 2 pHMnp

42

4 ])].[(.[][

1

eaqOHK

][

][lg

059,00

SP

PU

nEE

0591,0

EpE

][

][lg

10

SP

PU

npEpE

23

2

3

MgCaCO

CaMgCOk

olWSI VF )(

2

2

SWSDD

VACF

dVC

sD

24

DFF1

24

24

6)(

223 S

WS

WS

Vd

dVd

2118

dSg

V PS

2)(18

dg

V WSS

V

L

V

H

S

WH

QV

Q

V

Q

WHLt ol

S

ol

V

H

Q

V

PS

A

Q

LW

QV

SS V

V

LVV

LVV

ca

cbX 111

)/(

)/(

dxV

VXX

SX

SSr

0

)1(

dxV

VSX

S0

XVV

XXS

Sr

1)1(

2303312

36400mAP

W

QWOR

2)(18

dg

V WSS

2

3)0,115,1(

10002,118

81,9d

XS

t

HV

3126460

50

24

36400mx

25,5025

1264m

m1,105

5,50

2)(18

dg

V WPS

PA

QV1

PS A

QV

tkNdt

dN

ktN

Nt

0

ln

ktt eNN 0

61

110

50

61200][ 33HCO

*

32

31

]][[

COH

HCOHK

*

32

2

32

COH

COHK

1

3[HCOCT

]/[/][1

1

21

1 HKKH

93,010/)108,4()1047,4/(101

15,71175,7

lmolCT /1029,493,0

104 33

0A

5

9

9

5