CH 233 9

log f i-Azli x,$i

1 +Baj fi.‘.... (2.2)

(I) Samuel H. Maron and Carl F. Prutton, Principles of Physical Chemistry, 4ed. Collier-

Macmillan International Edition, 1969 MCI 434-443

10 CH 233

log f i = -A$ & . . . . . . (2.3)

log f i . ..*.. (2.4)

cc = c (xmZ + yn’ ) ( 2 . 6 )

OH 233 11

NaCl0.08 (d i-d) 0.08 %&.I Mxl

2

% so40.04(?x12 + 1x22) 0 . 1 2 #;a Mx

2R%dwi

HC, H,%

1aaJ 0.20

12 CH 233

-0.512 x I2 x &IT5log f i =

1+&T! ’

= -0.160.84

fi = ] o- 0.16 = 10 x lo-’= 6.9 x IO-'

= 0.69

logfi =~0.512 x 2243G

1+&z

x -0.62

fi = 10-0.62 = 1oo.38x lo-* = 2.4x1O-1

= 0.24

(f_,)m+ n = (f*)“(f,,” . . . . . . (2.7)

log fi = -0.512 z,z, fi. . . . . . (2.8)

1 + fi

CH 233 1 3

A+B =+ C tll (2.10)

“(‘“I~Kv

(2.1 I)

“A%

16 CH 233

(2.12)

(2.13)

(1.14)

(2.15)

17

(common ion effect)

@3J@iilc;l Kq YQJ A + B -- C + D ikiltv;ln'y 1 tttX~2lUtu'u&4

m [A],[B],[c] tt@r [D] eiiJtfiwiin”Y 0.5 M ~RU?A @i’~ju”~

Keq[ c I [ D 1 0.5 x 0.5= = = 1[AIIBI 0.5 x 0.5

18 CH 233

0 -r 8 3 P g. “. B

x II 0 L.

c-

--

m>

00

--

--

02

00

o-

‘E;A

L,

L,

,

+ +

x%

++

‘x

+

-x

x

x

aA ibH -+ PP+YQ ..,,,(2.19)

K =eq

K. fp fqP Q.-

f”lb .

(2.20)

A U

K = K,, ra cbq ‘A ‘B . (2.211

fP fqP Q

log K = log Keq - a log fA - b log fB + p log fp + q log fQ

vlia

pK = pK’- a log fA - b log fs + p log fp + q log fQ ( 2 . 2 2 )

pK= pKeq+0.S12(aZ~ + b Z; -XfF

P Z;, - q Z; ) 1+=(2.23)

A, B, _--* mA”+ + nB”‘- ( 2 . 2 4 )

WlRUfll3~ 2.23

$2 = PKeq, + 0.512 ( 1 X 2: -HCO;

1x? - 1 x zLo= ) xHz0 3

fi

1+4-z

= 10.33 + 0.512 ( 1 X l2 .- 1 Xl2 - 1x2yx m

1+qimG

= 10.33 - 2 ( 0.183 )

= 9.96

CH 233 21

j . . . . . . . . . (2.26)

22 CH 233

log K= - A H ”

K,(!- ‘1

2.303R T( R =0.001987 KCal / ‘KKmole)

7T

1

log K* -40.9 (1 1- )--__ ‘,5.61 2.303 x 0.001987 1173 1073

log K, - 0.749 = - 8.94 x ld’( 8.52 x 14-4 - 9.32 X lo-’ ) ’

= - 8.94 X lo3 ( - 0.80 X 1O-4 )

= 1.464

K2 = 29.1

CH 233

T, = 667°K

T, = 760 “K

K, = 0.0162

23

ud 2

LdQtLYlWildlJ 7 RJbWJfd (2.26)

In K2(0.0162)

= 0.276

In K2 2.303 log K*(0.0162) =

- = 0.276(0.0162)

log K2 0.276

(0.0162) = ~2.303

K2(0.0162) = "32

K, = 0.0214

24 CH 233

wJ;t 1 2so2 (9) + O2 (g) e =O,(g)

CH 233 25

mi 2

26 CH 233

LhiiJfiaJqa~bn~sil [Fe'+] + [Fe3+] = 0.200 M

[ t;e3+1 = 0.200 0.173

= 0.027 M

ri0~~~~~~~3~iiifl~l~b~~~~UQ~ [ I- I = 0.300 M

dQhJ~A"tGldl [ I- I + 3[ ‘3 1 = 0.300

[ I- 1 = 0.300 - 3 (0.0866)

= 0.040 M

Kv= (0.173)*(0.0866)

(0.027)'(0.040)3

= 5.55 x lo4

CH 233 27

uni 2

2HF(s) + Hz (9) + Fz cd

(1)

1 HFcg) 1 + [ Hzcgj I + I Qgj 11.00ha

= - = 0.500 M . .~.QOREI.RBJ.

(2)

r’ HF(d I + 2[ F2(g) 1 = 0.500 M . . . (3)

[ HF(d 1 = 0.500 - 2[ Fz(g) ] ( 4 )

ttnufi~ (4) FGII.J (1)

K= ’ FQJ I2

(0.500-2[ F, (g$= 1.00 x 10-13

[ F&d I2 =(o.500)2

1 .oo x lo- l3

[ F,(g) ]2 = (1 .00 x 10-13) (0.2500)

= 2.50 x lo-l4

W(g)] = 1.58 x lO-7 M

28 CH 233

4. .asni

[ c1,(g) ] Lii”h4 = x

tW$iilfJ

[ PC15 (g) 1 = 0.050 - x

1 pc13(g) 1 = 5.00 +x

[ .q 1 [ Cl, I = (5.00 +x1 (xlK =

= 33.3eq I PC& 1 (0.050 - x)

x << 5.00

(5.00) x =(0.050-x)

5.00 x =

38.3 x =

x = [ Cl, I=

[ q I=

=

1 PC& 1

33.3

1.67 - 33.3 x

1.67

0.0435 M

0.050-x =0.050-0.0435

0.0065 M

5.00+x =5.00+0.0435

5.04 M

CH 233 29

HA + Hz0 = HI0 + A- (2.27)

C = 0.02H A

= [ HA ] + [ A- ] ( 2 . 2 8 )

H,A f H,O =i=+ H A - + Hz0 (2.29)

HA- + H,O =i+ A=+ H+O3 (2.30)

C%A

= [ H,A ] + [ HA-] + [ A=] . (2.31)

30 CH 233

[ Na+] = 0.30

CH 233 31

un4 2

2H,O H H;O + O H - . . . (2.34)

[ H:O 1 = [ OH- ] . . . . . (2.35)

2H,O G=+ Hz0 + O H - . . . . (2.37)

Na, CO, e 2Na+ + COY . . . (2,38)

32

co; + y,o G- H C O , + O H - . , . . (2.39)

CH 233

[ Na+ ] + [ H;O ] = [ OH- ] + [ HCO; ] + 2 [ CO; ] (2.41)

I-PO:- + H,O e H,PO, + OH-

H, PO; + H,O e H3po‘l + OH-

2H,O =S H;O + OH-

CH 233 3 3

:. CBE &Y

CaC, 0 , - C a Z+ tc,o,

C,O~ +H,O + HC,O, +OH-

HC,O, +H,O + H,C,O, +OH-

2H?O F+ H;O +OH-

:. CBE &I

[H:O] + +A*+] = [ OH- ] + [ HC,O, ] + 2 [ C,O,= ]

2H, 0 c+= H:O + OH-

:. CBE $0

[H;Ol + [K+l = [ O H - ] + 3[Fe(CN):-]

3 4 CH 233

2H20 c+ Hz0 + OH

H,po4 + Hz0 + Hz0 + H,PO,

H, PO, + H,O =i+ HI0 + HPO,

H P O , + H,O + H;O + PO:

CH 233 35

unA 2

H,PO; + H,O s=+ H,PO, + OH-

HPO:- + H,O G== H,PO; + OH-

2H,O =i== HP + OH-

36 CH 233

HPO; - + I-1, 0 ;=-lt Hz PO I4 011

HPOZ, - + II,0 i Hp I IY(

2H, 0 = Ii:0 1 OII

:. I’BE %I

[ Hz0 ] + [ HzPO; ] + .1 1 1171’0, 1 [ OIIm 1 + 1 lWm ]

FI,C204 + I-1,0 c==+ II:0 + lK20;

HcI 0; + H,O --‘ tl;O + c,o,=

2 H,O i=-k t1:o t 011-

NH, +H,O =i+ NH; +Oli

CH 233 3 7

x(x +a)’ = K . . . _ . . (2.46)

x2($ +a) = K

x2 (a) = K

x

38 (‘H 233

CH 233 7”I .”

x(0.01 00 + x)--___~~~ = 0.00050(0.0100 -x)

x, (0.0100) = 0.0005~(0 .Ol 00 1

(0.0100 + 0.00050)

X2 (0.0100 - 0.00050)= 0.00050

40

5zz 0.0004~5

CH 233

~l?&XJI’U~~-9~ 3 (Third approximation)

(0.0100 + 0.00045)x _.~.~---. -

3= 0.00050

(0.0100 0.00045)

X3 = 0.00046

~II~~XUXM~~-S~ 4 (Fourth approximation)

(0.0l00 + 0.00046)h4 - -= 0.0005

(0.0100 -- 0.00046)

‘ 4 = 0.00046

ap4” S = fllX3ttWJb?.h&bURlill~9 Ag2Cr04 1I-k 0.00030 M K2Cr04

[ Ag+ j = 1s

1 cm, j = s t 0.00030

&(s+0.00030) = I .70 Y lo-'*

fmhmlmk~ 1 0.00030 >>> s

(2S,)2(0.00030) = 1.29 x IO- I2

s, = 0.33 x lo-4 M

93%%4-h 0.00030 > s, bhi nib

CH 233 41

(3, ) (o.i;Ylo zi t 0.0;,0.q)) : I.29 s IO-‘?

s- : Oil Y !omi

(7s,)2 (0.31x10~~~+0.00030) = 1.21) s lo-‘?

K10, &&q = 3.00 - (2 x 1.4)

= 0.2 EaB%sJa

42 CH 233

CH 233 4 3

&=q&l s # 0.5 x 10-x

aala,la=tt x - 0 . 4 x 10 3

1.3 x 10-g 1.57 x 1o-9 = -0.3 x lo-’

4 4 CH 233

CH 233 45

46 CH 233

11;

72)

! 3)

IJWG 2

b) '8l~F-l~'8JllQ9 0.02 M NaCl LbRt 0.03 M NaNO,

c) k3l~KiTlUWtT3JllQ9 0.05 M NaCIO, l,bcqz 0.03 M HC1

16) BSQil~a61b95l~l~~BJPJ~~~prl~~;aaQn83~aa~er (ff) WI9 0.200 F CaC12 (WIII 0.161)

1 7r, blUllldkJfll~~ 2.4, 2.5, 2.7 b1RtWlSl9ti 2.1 'N~l~~slb~ldl~~d~"~~~

bLQ+lQ31 L&l (f +) vosbn8owdaralulua?*~~~~~~~~~~

a) 0.0250 F Ca12 au27 OlQLl 0.630

b) 0 . 0 0 1 0 0 F BaC12 ~U~lXX3lLi 0 . 0 3 0 0 F WQIJ 0 . 7 0 8KN03

c) 0.0050 F AIC$ 'LUtTlXX3ltl 0.0100 F NaN03 @lQlJ 0.603

d) 0.0150 F NaHC03 au& BlQY 0.884

e) 0.0300 F K2Cr04 ~P~~~XW~JU~JVQ~ 0.100 F NaOH k&E 0.200 -

F LiC103 FIQ¶J 0.242

b ) Na,HPO, e) MgKW, h ) NaHCO,

c) H,S f ) NH,CI i) K, cro,

a ) H,S d ) N H , d H,CO,

b ) Hz S O , c) NH, Cl h) HCOOH

c ) Na,HPO, f) CH, COONH, i) KCN

48 CH 233