ch 233 9 - old-book.ru.ac.thold-book.ru.ac.th/e-book/c/ch233/ch233-2.pdf · -0.512 x i2 x &it5...
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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