UNDERWOOD

1. Koefisien distribusi (a) seorang ahli kimia melarutkan 55,13 mg iodin (I2 ) dalam tepat 1
liter air distribusi.. disetimbangkan pada 25o C dengan tepat 50 ml CCl4. Titrasi pelarut
organik membutuhkan 22,35 ml larutan Na2S2O3 0,04474 M (reaksi titrasi 2 S2O32- + I2
S4O62- + 2I-). Hitung KD untuk I2 antara kedua zat tersebut (CCl4 / H2O). (b) Natrium
tiosulfat adalah garam yang mudah larut dalam air. Jelaskan bagaimana menitrasi I2 dalam
sebuah larutan CCl4 dengan suatu larutam besar Na2S2O3.
Jawaban :
- 2 e- + I2 = 2I- ( 1mol I2 = 2eq)
- 2 S2O32- = S4O62- + 2e- (1 mol S2O32- = 1 eq)
Syarat : mol. Ek I2 = mol Ek S2O32-
mol. Ek I2 = N. V
mol. Ek I2 = (0,04474N) (22,35 ml)
mol. Ek I2 = (0,9999 mmolek):2
mol I2 (org) = 0, 4999 mmol
- Mol I2 (mula-mula) = (55,13 mg) : 253,8
= 0,61123 mmol
- n I2 (aq) = n I2 (mula-mula) – n I2 (org)
= 0,11133 mmol

0,4999 𝑚𝑚𝑜𝑙
[𝐼2 ]𝑜 50 𝑚𝑙
- KD = [𝐼 }𝑎𝑞 = 0,11133 𝑚𝑚𝑜𝑙 = 89,8
2
1000 𝑚𝑙

2. Ekstraksi (a) jika 50 ml I2 encer 0,00100M diekstraksi dengan 50 ml CCl4. Hitung berapa
presentasi I2 yang di pindahkan dari fasa berarir tersebut (gunakan KD dari soal 1) (b) ulangi
dengan ekstraksi berturut-turut dengan 25 ml CCl4
Jawaban :
- Diketahui : Vaq = 50 ml
VCCl4 = 50 ml
KD = 89,8
- Ditanya : %E ?
- Jawab :
50 𝑚𝑙
(a) 1-forg = ( )
50 𝑚𝑙+89,8 𝑥 50 𝑚𝑙

forg = 0,9889
%E = 98,89 %
𝑉𝑎𝑞
(b) faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔
 50 𝑚𝑙
1-forg = ( )2
50 𝑚𝑙+89,8 𝑥 50 𝑚𝑙
50 𝑚𝑙 2
1-forg = ( )
54,49 𝑚𝑙
1-forg = (0,011)2
1-forg = 1,21 x 10-4
forg = 0,9998
%E = 99,98 %

3. Rasio distribusi (a) bila suatu larutan berair FeCl3 dalam HCl pekat dikocok dengan eter
dengan volume 2 kali larutan itu yang mengandung HCl 99% besi itu tereksitasi. Hitunglah
angka banding distribusi (organik/berair) daari Fe (III). (b) Besi (III) dapat dipisahkan dari
logam-logam lain seperti kromat dengan ekstraksi kedalam ater dari dalam suatu larutan
berair HCl yang kuat . Jika 75 ml HCl berarir yang mengandung 0,390 gram Fe (III) itu di
olah dengan 100 ml eter dalam suatu proses satu tahap, beraa miligram besi tertinggal
dalam ase tersebut.
Jawaban :
- Diketahui : Vaq = V
Vorg = 2V
HCl =99%
- Ditanya : D?
- Jawab :
100 𝐷
%E = 𝑉𝑎𝑞
𝐷+𝑉𝑜𝑟𝑔

100 𝐷
99 = 𝑉
𝐷+2𝑉

100 𝐷
99 =
𝐷+0,5
D = 0,495
4. Ekstraksi basa lemah. Dalam bentuk “basa bebasnya”, kokain (BM 303,4) merupakan
amin tersier dengan Kd sekitar 2,6 × 10-6 (pKb = 5,59). Dalam laboratorim pengujian obat,
kokain kadang diekstraksi dari sampel urin alkalin menjadi eter; residu setelah penguapan
eter itu kemudian diperiksa dengan suatu teknik kromatografi, seringkali kromatografi
lapisan-tipis. (a) pH urin (berbeda dengan darah) bervariasi dan sangat tergantung pada
diet; ini biasanya pada sisi asam dan bisa sampai serendah 4,5. Mengapa sampel urin
tersebut diolah dengan alkali sebelum terekstraksi? [Jelaskan secara kualitatif, dalam kata-
kata; lihat bagian (c) untuk perhitungan.] (b) Menurut salah satu buku pegangan, 1 g kokain
akan larut dalam 600 mL air dan dalam 3,5 mL eter. Hitung Kd. (c) Hitung rasio distribusi
(D) kokain pada nilai pH berair 5, 6, 7, 8, 9, 10, 11, dan 12, dan plot D vs pH. Bandingkan
data aktual dengan konsep kualitatif dalam bagian (a); apakah data tersebut sesuai dengan
“gambaran” berdasarkan firasat kimia Anda?
Penyelesaian :
- Diketahui :
BM kokain = 303,4 g/mol
Kd = 2,6 × 10-6
pKb = 5,59
Massa kokain = 1 g
Va = 600 mL
Vo = 3,5 mL
- Ditanya :
a. Mengapa sampel urin tersebut diolah dengan alkali sebelum ekstraksi?
(Jelaskan secara kualitatif, dalam kata-kata)
b. Hitung Kd?
c. Hitung D kokain pada pH berair 5, 6, 7, 8, 9, 10, 11, dan 12 dan buat plot D
vs pH?
- Jawab :
a. Urine mengandung suatu senyawa yang dinamakan asam urat. Asam urat adalah
hasil akhir yang penting dalam oksidasi urine yang sukar larut dalam air, tetapi
membentuk garam yang larut dalam alkali. Oleh karena itu asam urat mudah
mengendap dalam urine bila dibiarkan. Pengolahan urine dengan alkali
bertujuan untuk melarutkan garam-garam yang terbentuk dari senyawa asam urat
sehingga garam tersebut dapat diekstraksi dan dipergunakan sebagai sampel
suatu pengujian tertentu.
b. Dalam air
𝑀𝑎𝑠𝑠𝑎 𝐾𝑜𝑘𝑎𝑖𝑛 1000
Ca = ×
𝑀𝑎𝑠𝑠𝑎 𝑀𝑜𝑙𝑎𝑟 𝑉𝑎
1𝑔 1000
= ×
303,4 𝑔/𝑚𝑜𝑙 600
= 5,4932 × 10-3 M
Dalam eter
𝑀𝑎𝑠𝑠𝑎 𝐾𝑜𝑘𝑎𝑖𝑛 1000
Co = ×
𝑀𝑎𝑠𝑠𝑎 𝑀𝑜𝑙𝑎𝑟 𝑉𝑜
1𝑔 1000
= ×
303,4 𝑔/𝑚𝑜𝑙 3,5
= 0,9417 M
𝐶𝑜
Kd =
𝐶𝑎
0,9417
=
5,4932 × 10−3
= 171,4301
c. pH = 5 ; pOH = 9 ; [OH-] 𝐾𝑑
D = 𝐾𝑏
= 10-9 1+
[𝑂𝐻−]
𝐾𝑑 171,4301
D = 𝐾 =
1+ 𝑏− 2,6 ×10−6
[𝑂𝐻 ] 1+
10−5
171,4301 171,4301
= 2,6 ×10−6 =
1+ 1,26
10−9
171,4301 = 136,0556
=
2601
= 0,0659 pH = 10 ; pOH = 4 ; [OH-]
= 10-4
pH = 6 ; pOH = 8 ; [OH-] 𝐾𝑑
D = 𝐾𝑏
= 10-8 1+
[𝑂𝐻−]
𝐾𝑑 171,4301
D = 𝐾𝑏 =
1+ 2,6 ×10−6
[𝑂𝐻−] 1+
10−4
171,4301 171,4301
= 2,6 ×10−6 =
1+ 1,026
10−8
171,4301 = 167,0858
=
261
= 0,6568 pH = 11 ; pOH = 3 ; [OH-]
= 10-3
pH = 7 ; pOH = 7 ; [OH-] 𝐾𝑑
D = 𝐾𝑏
= 10-7 1+
[𝑂𝐻−]
𝐾𝑑 171,4301
D = 𝐾𝑏 =
1+ 2,6 ×10−6
[𝑂𝐻−] 1+
10−3
171,4301 171,4301
= 2,6 ×10−6 =
1+ 1,0026
10−7
171,4301 = 170,9855
=
27
= 6,3492 pH = 12 ; pOH = 2 ; [OH-]
= 10-2
pH = 8 ; pOH = 6 ; [OH-] 𝐾𝑑
D = 𝐾𝑏
= 10-6 1+
[𝑂𝐻−]
𝐾𝑑
D = 𝐾𝑏
171,4301
1+ = 2,6 ×10−6
[𝑂𝐻−] 1+
171,4301 10−2
= 171,4301
2,6 ×10−6 =
1+ 1,00026
10−6
171,4301 = 171,3855
=
3,6
= 47,6194

pH = 9 ; pOH = 5 ; [OH-]
= 10-5
 Plot D vs pH
200.0000
180.0000
160.0000
140.0000
120.0000
100.0000
D

80.0000
60.0000
40.0000
20.0000
0.0000
0 2 4 6 8 10 12 14
pH

5. Koefisien distribusi tiga ekstraksi dengan porsi 25 ml suatu pelarut organik

menyingkirkan 96% suatu zat terlarut dan 100 ml larutan berair. Hitunglah koefisien
distribusi ( org/air) dari zat terlarut itu.
Jawaban :
- Diketahui : % E = 96 %
Vaq = 100 ml
- Ditanya : KD?
- Jawab :
𝑉𝑎𝑞
faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔

100 𝑚𝑙
0,04 = ( )3
100𝑚𝑙+𝐾𝐷 .25𝑚𝑙

3 100𝑚𝑙
√0,04 = 100𝑚𝑙+𝐾
𝐷 .25𝑚𝑙

0,342(100 𝑚𝑙 + 𝐾𝐷 . 25 𝑚𝑙) = 100 ml

KD = 7,69
6. Ekstraksi berganda koefisien distribusi suatu zat terlarut S antaea benzena dan air
adalah 12,0 (org/air). Hitung presentasi S yang tereksittasi kedalam benzena dari 50 ml
larutan berair S 0,1 M. Jika ekstraksi itu dilakukan dengan (a) Satu porsi 50 ml benzena
(b) 2 porsi 25 ml larutan benzena (c) lima porsi 10 ml benzena
Jawaban :
- Diketahui : KD = 12,0
Vaq = 50 ml 0,1 M
- Ditanya : (a) %E Satu porsi 50 ml benzena
(b) %E 2 porsi 25 ml larutan benzena
 (c) %E lima porsi 10 ml benzena
- Jawab :
𝑉𝑎𝑞
a) faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔
50 𝑚𝑙
=( )1
50 𝑚𝑙+(12).50𝑚𝑙

faq = 0,0769
forg = 1- f aq
= 1-0,0769 =0,923
%E = 92,3 %
𝑉𝑎𝑞
b) faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔
50 𝑚𝑙
=( )2
50 𝑚𝑙+(12).25𝑚𝑙

faq = 0,0204
forg = 1- f aq
= 1-0,0204 =0,9796
%E = 97,96%

𝑉𝑎𝑞
C) faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔
50 𝑚𝑙
=( )5
50 𝑚𝑙+(12).10𝑚𝑙

faq = 2,2 x 10-3

forg = 1- f aq
= 1-2,2 x 10-3=0,9979
%E = 99,79 %
7. tetapan disosiasi asam dan rasio distribusi. Suatu asam HB mempunyai koeffisien
distribusi 9,8 antara pelarut organik dan air. Pada pH 5 tepat separuh bahan tereksitasi
kedalam pelarut organik dan dalam fasa berair yang sama. Hitunglah tetapan disosiasi
HB
Jawaban :
- diketahui : Vaq=Vorg=V
%E = 50%
forg = 0,5
- ditanya : Ka dan D?
- Jawab :
 H2O + HB H3O+ + B-
Ka
 [𝐻3𝑂]𝑎𝑞 [𝐵]𝑎𝑞
Ka =
[𝐻𝐵]𝑜𝑟𝑔

100 𝐷
 %E = 𝑉𝑎𝑞
𝐷+
𝑉𝑜𝑟𝑔

100 𝐷
50 =
𝐷+1
D=1
[𝐻𝐵]𝑜𝑟𝑔
 D=
[𝐻𝐵]𝑎𝑞 +[𝐵]𝑎𝑞
[𝐻𝐵]𝑜𝑟𝑔
= 𝐾𝑎[𝐻𝐵]𝑜𝑟𝑔
[𝐻𝐵]𝑎𝑞 + [𝐻3𝑂]𝑎𝑞

𝐾𝐷
D= 𝐾𝑎
1+[𝐻3𝑂]𝑎𝑞

9,8
1= 𝐾𝑎
1+ −5
10

Ka =8,8 x 10-5
8. NO...
9. Ekstraksi suatu kelat logam. Suatu zat pengkelat HT, yang dilarutkan dalam suatu
pelarut organik mengekstrak suatu logam, M2+, dan dalam suatu larutan berair
menurut reaksi
2H2O + M2+(aq) + 2HTorg -> MT2org + 2H3O+(aq)
Tetapan kesetimbangan untuk reaksi ini adalah 0,10
a) Nyatakan tetapan kesetimbangan ini dalam tetapan lain
b) Hitunglah nilai pH pada 1%, 25%, 50%, 75%, dan 99,9% logam diekstraksi dari
10mL, dan berair dengan 10mL larutan HT 0,0010 M dalam pelarut organik.
(Asumsikan konsentrasi logam begitu kecil sehingga [HT]org tetap konstan).

Jawaban:

- Diketahui : 2H2O + M2+(aq) + 2HTorg -> MT2org + 2H3O+(aq)

- Ditanya : a. K
b. pH pada 1%, 25%, 50%, 75%, 99,9%
- Jawab :
𝐾𝑒𝑘𝑠 𝑥 [𝐻𝑥]𝑛 𝑜𝑟𝑔
a. 𝐷𝑚 = [𝐻2𝑂 + ]𝑛 𝑎𝑞

log Dm = log Keks + n loh [Hx]org + n pH

 𝑓 .𝑉𝑎𝑞
b. log(𝑉𝑜𝑟𝑔−𝑓 .𝑉𝑜𝑟𝑔) = log 0,1 x 2 (log 0,001) + 2pH

0,01 .(10)
log(10−0,01 .10)= -1 + (-6) + 2pH

0,1
log(9,9) = -7 + 2pH

pH = 2,502
𝑓 .𝑉𝑎𝑞
log(𝑉𝑜𝑟𝑔−𝑓 .𝑉𝑜𝑟𝑔) = log 0,1 x 2 (log 0,001) + 2pH

0,25 . 10
log(10−0,25 .10) = -7 + 2pH

2,5
log(7,5) = -7 + 2pH

pH =3,26
𝑓 .𝑉𝑎𝑞
log(𝑉𝑜𝑟𝑔−𝑓 .𝑉𝑜𝑟𝑔) = log 0,1 x 2 (log 0,001) + 2pH

0,5 . 10
log(10−0,5 .10) = -7 + 2pH

5
log(5) = -7 + 2pH

pH =3,5
𝑓 .𝑉𝑎𝑞
log( ) = log 0,1 x 2 (log 0,001) + 2pH
𝑉𝑜𝑟𝑔−𝑓 .𝑉𝑜𝑟𝑔

0,75 . 10
log(10−0,25 .10) = -7 + 2pH

7,5
log(2,5) = -7 + 2pH

pH =3,73
𝑓 .𝑉𝑎𝑞
log(𝑉𝑜𝑟𝑔−𝑓 .𝑉𝑜𝑟𝑔) = log 0,1 x 2 (log 0,001) + 2pH

0,999 . 10
log(10−0,999 .10) = -7 + 2pH

9,99
log( 0,1 ) = -7 + 2pH

pH =4,99

10. Ekstraksi suatu kelat logam. Ulangi soal 9 untuk suatu logam N2+ dimana tetapan
kesetimbangan untuk reaksi itu seperti dirumuskan di atas adalah 1,0 x 10-7. Plotkan
datanya seperti di atas dan pilihlah pH serendah mungkin untuk memisahkan M2+ dan
N2+.
- Diketahui :
2H2O + N2+(aq) + 2HTorg ↔ NT2 org + 2H3O+ (aq)
[𝑁𝑇2 ]𝑜 [H3 O+ ]𝑎
𝐾𝑒𝑥 =
[𝑁 2+ ]𝑎 [𝐻𝑇]2 𝑜

Diketahui :
Kex= 10-7
[HT]o = 10-3
Dari penurunan diperoleh :
𝐷𝑀[H3 O+ ]𝑎
𝐾𝑒𝑥 =
[𝐻𝑇]2 𝑜

𝐾𝑒𝑥 [𝐻𝑇]2 𝑜
𝐷𝑀 =
[H3 O+ ]𝑎
Ditanya : plot log DM vs pH
Penyelesaian :
 pH = 0
log DM = log Kex + 2 log[HT]o + 2 pH
= log 10-7 + 2 log 10-3 + 2(0)
= -7 – 6
= -13

 pH = 0,5
log DM = log Kex + 2 log[HT]o + 2 pH
= log 10-7 + 2 log 10-3 + 2(-0,5)
= -7 – 6 - 1
= -14

 pH = -1
log DM = log Kex + 2 log[HT]o + 2 pH
= log 10-7 + 2 log 10-3 + 2(-1)
= -7 – 6 - 2
= -15

 pH = -1,5
log DM = log Kex + 2 log[HT]o + 2 pH
= log 10-7 + 2 log 10-3 + 2(-1,5)
= -7 – 6 - 3
= -16

 pH = -2
log DM = log Kex + 2 log[HT]o + 2 pH
= log 10-7 + 2 log 10-3 + 2(-2)
 = -7 – 6 - 4
= -17
 pH = 1
log DM = log Kex + n log[HX]o - n log [H3 O+ ]𝑎
log 10-8 = log Kex + n log(10-2) - n log(10-1)
10−2
-8 = log Kex + n log 10−1
-8 = log Kex + log 10-n
-8 = log (Kex . 10-n)

 pH = 2
log DM = log Kex + n log[HX]o - n log [H3 O+ ]𝑎
log 10-8 = log Kex + n log(10-2) - n log(10-2)
10−2
-8 = log Kex + n log 10−2
-8 = log Kex + log 10n
-8 = log (Kex . 10n)

0
-2 -1.5 -1 -0.5 0
-2
-4
-6
log DM

-8
-10
-12
-14
-16
-18
pH

 pH = 1
𝐷𝑀[𝐻3 𝑂+ ]𝑛
𝐾𝑒𝑥 =
[𝐻𝑋]𝑛
10−8 (10−1 )4
=
(10−2 )4
10−8 . 10−4
=
10−8
-4
= 10

 pH = 2
 𝐷𝑀[𝐻3 𝑂+ ]𝑛
𝐾𝑒𝑥 =
[𝐻𝑋]𝑛
10 (10−2 )4
−4
=
(10−2 )4
10−4 . 10−8
=
10−8
-4
= 10

 pH = 3
𝐷𝑀[𝐻3 𝑂+ ]𝑛
𝐾𝑒𝑥 =
[𝐻𝑋]𝑛
101 (10−3 )4
= 10
(10−3 )4
8
101 . 10−12
= 6
10−8 4
-4
= 10
2
log DM

0
 pH = 4 1 2 3 4 5
-2
𝐷𝑀[𝐻3 𝑂+ ]𝑛
𝐾𝑒𝑥 = -4
[𝐻𝑋]𝑛 -6
104 (10−4 )4 -8
=
(10−2 )4 -10
pH
104 . 10−16
=
10−8
-4
= 10
 pH = 5
𝐷𝑀[𝐻3 𝑂+ ]𝑛
𝐾𝑒𝑥 =
[𝐻𝑋]𝑛
10 (10−5 )4
8
=
(10−2 )4
108 . 10−20
=
10−8
-4
= 10

11. Ekstraksi suatu kelat logam. Suatu ion logam tertentu diekstraksi oleh suatu zat
pengkelat seperti dalam soal no 9 dan 10. Konsentrasi zat pengkelat dalam fasa organik
adalah 0,010 M. Diperoleh data berikut :
pH 1 2 3 4 5
D 10-8 10-4 1 104 108
Plotkan log vs pH dan carilah nilai n dan Kex
Jawaban:

pH =1
 𝐷𝑚 [𝐻3 𝑂+ ]𝑛 10−8 (10−1 )4
𝐾𝑒𝑥 = 𝑛
= −2 4
= 10−4
[𝐻𝑋] (10 )
pH = 2
𝐷𝑚 [𝐻3 𝑂+ ]𝑛 10−4 (10−2 )4
𝐾𝑒𝑥 = = = 10−4
[𝐻𝑋]𝑛 (10−2 )4
pH = 3
𝐷𝑚 [𝐻3 𝑂+ ]𝑛 (10−3 )4
𝐾𝑒𝑥 = = = 10−4
[𝐻𝑋]𝑛 (10−2 )4
pH = 4
𝐷𝑚 [𝐻3 𝑂+ ]𝑛 10−4 (10−4 )4
𝐾𝑒𝑥 = = = 10−4
[𝐻𝑋]𝑛 (10−2 )4
pH = 5
𝐷𝑚 [𝐻3 𝑂+ ]𝑛 108 (10−5 )4
𝐾𝑒𝑥 = = = 10−4
[𝐻𝑋]𝑛 (10−2 )4

pH =1
log 𝐷𝑚 = log 𝐾𝑒𝑥 + 𝑛 log[𝐻𝑋] − 𝑛 log[𝐻3 𝑂]+
log 10−8 = log 𝐾𝑒𝑥 + 𝑛 log 10−2 − 𝑛 log(10−1 )
10−2
−8 = log 𝐾𝑒𝑥 + 𝑛 log
10−1
−8 = log 𝐾𝑒𝑥 + 𝑛 log 10−1
−8 = log 𝐾𝑒𝑥 + log 10−𝑛
−8 = log(𝐾𝑒𝑥. 10−𝑛 )

pH = 2
log 𝐷𝑚 = log 𝐾𝑒𝑥 + 𝑛 log[𝐻𝑋] − 𝑛 log[𝐻3 𝑂]+
log 10−4 = log 𝐾𝑒𝑥 + 𝑛 log 10−2 − 𝑛 log(10−2 )
10−2
−4 = log 𝐾𝑒𝑥 + 𝑛 log
10−2
−4 = log 𝐾𝑒𝑥 + 𝑛 log 101
−4 = log 𝐾𝑒𝑥 + log 10𝑛
−4 = log(𝐾𝑒𝑥. 10𝑛 )
 Plot pH 1 dan pH 2
−8 = log 𝐾𝑒𝑥 + 𝑛 log 10−1
−4 = log 𝐾𝑒𝑥 + 𝑛 log 101
−4 = 𝑛 log 10−1
−4 = −𝑛
4=𝑛

10
8 y = 4x - 12.2
R² = 0.995
6
4
2
Log Dm

0 log Dm
-2 0 2 4 6 Linear (log Dm)
-4
-6
-8
-10
pH

12. Ekstraksi craig. Koefisien distribusi untuk ekstraksi zat terlarut A dari dalam air
kedalam suatu pelarut organik adalah 10 (organik/air) A sebanyak 1 gram dilarutkan
dalam air dan ditaruh dalam tabung o dari suatu alat ekstraksi craig dan diekstraksi
dengan pelarut organiknya. Fasa organik itu dipindahkan dari dalaam tabung 0 ke
tabung 1, dan seterusnya. (a) hitunglah fraksi A yang tetap berada dalam tabung 0
setelah lima transfer. (b) Hitunglah fraksi A dalam tabung 1,2,3,4, dan 5
Jawaban:
- Diketahui : KDA = 10 org/air
WA = 1 gram dalam tabung 0
- Ditanya :
a. fA dalam tabung 0 setelah lima transfer
b. fA dalam tabung 1,2,3,4,5
- Jawab :
1 𝐸 5
a. fA0 = ( + )
1+𝐸 1+𝐸
1 10 5
fA0 = ( + ) =1
1+10 1+10
b. fA dalam tabung 1,2,3,4,5
 𝑛!𝐾𝑏
 fn,r =
𝑟!(𝑛−𝑟)!(1+𝐾𝐷 )𝑛
5!(10)
f5,1 = = 3,1 x 10-4
1!(5−1)!(1+10)5
 5!(10)
f5,2 = = 6,2 x 10-4
2!(5−2)!(1+10)5
 5!(10)
f5,3 = = 6,2 x 10-4
3!(5−3)!(1+10)5
 5!(10)
f5,4= = 3,1 x 10-4
4!(5−4)!(1+10)5
𝑉𝑎𝑡𝑎𝑠
 E = KD x
𝑉 𝑏𝑎𝑤𝑎ℎ
0,03125
= 10 x = 10
0,03125
1 10 5
 fA5 = ( + ) =1
1+10 1+10

13. Ekstraksi Craig. Ulangi soal 12 kecuali bahwa nilai KD sekarang adalah 100.
1 𝐸 5
a. fA0 = ( + )
1+𝐸 1+𝐸
1 100 5
fA0 = ( + ) =1
1+100 1+100
c. fA dalam tabung 1,2,3,4,5
𝑛!𝐾𝑏
 fn,r =
𝑟!(𝑛−𝑟)!(1+𝐾𝐷 )𝑛
5!(100)
f5,1 = = 4,75 x 10-10
1!(5−1)!(1+100)5
 5!(100)
f5,2 = = 9,5 x 10-8
2!(5−2)!(1+100)5
 5!(100)
f5,3 = = 9,5 x 10-8
3!(5−3)!(1+100)5
 5!(100)
f5,4= = 4,75 x 10-4
4!(5−4)!(1+100)5
𝑉𝑎𝑡𝑎𝑠
 E = KD x
𝑉 𝑏𝑎𝑤𝑎ℎ
0,03125
= 100x = 100
0,03125
1 100 5
 fA5 = ( + ) =1
1+100 1+100
PECSOK
3-1 What is the minimunm value of KD which would allow the extraction of 99.9% of a
solute from 50 ml off water with successive 50 ml portions of ether?
Jawaban:
- Diketahui : %𝐸 = 99,9% (5x ekstraksi)
𝑓(𝑎) = (100 – 99,9)% = 0,1 % = 10-3
𝑉(𝑎) = 50 mL
𝑉(𝑂) = 50 mL
- Ditanya: 𝐾𝐷 ........... ?
- Jawab :
𝑉(𝑎)
𝑓(𝑎) = (𝑉 )𝑛
(𝑎) +𝑉(𝑜) 𝐾𝐷
50
10−3 = (50+50𝐾 ) 5
𝐷
5 50
√10−3 = 50+50𝐾𝐷
50
0,25 = 50+50𝐾𝐷
12,5 + 12,5𝐾𝐷 = 50
12,5𝐾𝐷 = 37,5
37,5
𝐾𝐷 = 12,5
𝐾𝐷 = 3

3-2 If five extraction with 100 ml portion of extract 90% of asolute an aquoeus solution,
what fraction of the solute will ten similiar extraction remove ?
Jawaban:
- Diketahui :
V (o) = 100 Ml
%e = 90% = 0,9
Faq = 1 – 0,9 = 0,1
V(a) = 50 mL
- Ditanya :
F ............... ?
- Jawab :
100 𝐷
𝐸 = 𝑉 (𝑎)
𝐷+
𝑉 (𝑜)
100 𝐷
0,9 = 𝐷+1
0,9 D + 0,9 = 100 D
99,1 D = 0,9
D =9,08 x 10-3]

𝑉 (𝑎)
𝑓=( )5
𝐷𝑉 (𝑜) + 𝑉 (𝑎)
 50
𝑓=( )5
9,8 𝑥 10−3 (50) + 50
50
𝑓=( )5
50, 00454
𝑓 = 0, 99 𝑥 100%
𝑓 = 99 %

3-3 Drive an expression similar to Equation 3-10 for the distribution of pyridine between
water and benzene :
𝐶 5H5N + H+ = 𝐶 5H5NH+ ( in water )
𝐉𝐚𝐰𝐚𝐛𝐚𝐧 ∶
Distribusi dari piridin dalam air dan benzene
𝐶 5H5N + H+ = 𝐶 5H5NH+ ( dalam air)
[𝐶5 𝐻5 𝑁]𝑜𝑟𝑔
 KD = [𝐶5 𝐻5 𝑁]𝑎𝑞
[𝐶5 𝐻5 𝑁𝐻 + ][𝐻 + ]
 Ka = [𝐶5 𝐻5 𝑁]
+ [𝐶5 𝐻5 𝑁]
[𝐶5 𝐻5 𝑁𝐻 ] = Ka
[𝐻 + ]

Piridin dalam air mengalami reaksi

𝐶 5H5N + H+ ↔ 𝐶 5H5NH+
Dalam benzene akan mengalami dinerisasi
2 𝐶5 𝐻5 𝑁 ↔ 𝐶5 𝐻5 𝑁. 𝐶5 𝐻5 𝑁
[𝐶5 𝐻5 𝑁. 𝐶5 𝐻5 𝑁]
KD = [𝐶5 𝐻5 𝑁]2

𝐶𝑡𝑜𝑡𝑎𝑙 𝑝𝑖𝑟𝑖𝑑𝑖𝑛 𝑜𝑟𝑔 [𝐶5 𝐻5 𝑁]𝑜𝑟𝑔 + 2 [𝐶5 𝐻5 𝑁. 𝐶5 𝐻5 𝑁]𝑜𝑟𝑔

D = =
𝐶𝑡𝑜𝑡𝑎𝑙 𝑝𝑖𝑟𝑖𝑑𝑖𝑛 𝑎𝑞 [𝐶5 𝐻5 𝑁]𝑎𝑞 + [𝐶5 𝐻5 𝑁𝐻 + ]𝑎𝑞

[𝐶5 𝐻5 𝑁]𝑜𝑟𝑔 + 2𝐾𝐷 [𝐶5 𝐻5 𝑁]2

= [𝐶5 𝐻5 𝑁]𝑎𝑞
[𝐶5 𝐻5 𝑁]𝑎𝑞 + Ka
[𝐻+ ]
[𝐶5 𝐻5 𝑁]𝑜𝑟𝑔 (1+2 𝐾𝐷 [𝐶5 𝐻5 𝑁]𝑎𝑞
= 𝐾𝑎
[𝐶5 𝐻5 𝑁]𝑎𝑞 (1+ )
[𝐻+ ]
(1+2 𝐾𝐷 [𝐶5 𝐻5 𝑁]𝑜𝑟𝑔
D = 𝐾𝑎
(1+ )
[𝐻+]

3-4 In the craig process, some of the solute remains in the vesel no matter how many
transfers are made. Assuming that Vs = Vm, and that KD =1, what fraction of the solute
will remain in the first two vessels after ten transfers ?
Jawaban:
 - Diketahui : Vs=Vm=1
KD = 1
- Jawab
𝐾𝐷 𝑥 𝑉𝑠 1𝑥1 1
p= = =
𝐾𝐷 𝑥 𝑉𝑠 + 𝑉𝑚 1𝑥 1+ 1 2
𝑉𝑚 1 1
q= = =
𝐾𝐷 𝑥 𝑉𝑠 + 𝑉𝑚 1+ 1 2

3-5 A sample containing approximately 1 gram off organic substance. A is dissolved in 100
ml of water. The aqueos solution is then shalen with 100 ml of ether. Analysis of ether
layer shows that 0,7gram of A is extracted.
𝐶𝑒𝑡
a. What is the value of KD = for this system
𝐶𝑎𝑞
Jawaban :
Diketahui : Wo = 1 gram
Vaq = 10 ml
Vorg = 100 ml
forg = 0,7 gr
Ditanya KD = . . . ?
Jawab :
𝐶𝑒𝑡
KD =
𝐶𝑎𝑞
𝑉𝑎𝑞
faq = ( )1 x W o
𝑉𝑎𝑞 + 𝐾𝐷 (𝑉𝑜𝑟𝑔 )
100 𝑚𝑙
1 - faq = ( 100 𝑚𝑙+𝐾𝐷(100 𝑚𝑙) )1 x 1 gram
100 𝑚𝑙
1- 0,7 gram = ( 100 𝑚𝑙+ 𝐾 )1 x 1 gram
𝐷 (100 𝑚𝑙)

0,3 gram ( 100 ml + KD (100 ml)) = 100 ml (1 gram)

30 ml gram + 30 ml . KD = 100 ml gram
KD = 2,33
b. How many addition extraction with 100 ml portions of ether would be requred to
extract 95 % of the substance ?
Jawaban :
Diketahui : Vorg = 100 ml
Forg = 95 %
Ditanya n = . . . ?
 Jawab :
𝑉𝑎𝑞
faq = (𝑉 )n x Wo
𝑎𝑞 + 𝐾𝐷 (𝑉𝑜𝑟𝑔 )

𝑉𝑎𝑞
1-0,95 = (𝑉 )n x 1 gram
𝑎𝑞 + 𝐾𝐷 (𝑉𝑜𝑟𝑔 )

100 𝑚𝑙
0,05 = ( 100 𝑚𝑙+(2,33)(100 𝑚𝑙) )n x 1 gram
𝑛 100 𝑚𝑙
√0,05 = x 1 gram
100 𝑚𝑙+233 𝑚𝑙
𝑛 100 𝑚𝑙
√0,05 = x 1 gram
333 𝑚𝑙
𝑛
√0,05 = 0,3 𝑚𝑙
0,3 log 0,05 =n
log 0,05
=n
log 0,3

n = 2,5
c. What fraction of would have been extracted by four 25-ml pertions of ether?
Jawaban :
𝑉𝑎𝑞
faq = (𝑉 )4 x Wo
𝑎𝑞 + 𝐾𝐷 (𝑉𝑜𝑟𝑔 )

𝑉𝑎𝑞
1 – forg = (𝑉 )4 x Wo
𝑎𝑞 + 𝐾𝐷 (𝑉𝑜𝑟𝑔 )

100 𝑚𝑙
1 – forg = ( 158,25 𝑚𝑙 )4 x 1 gram

1 – forg = (0,632)4
1 – forg = 0,16
forg = 0,84
forg = 84 %

3-6 The distribution coefficient of organic compound is KD = Caq /Cpent =5.0. A 0.55 g sample
is placed in vessel 0 of a Craig apparatus. Each vessel holds 4 ml of water and 4 ml of
pentane (the lighter solvent which is transfered). Calculate the fraction of the compound
which is in each vessel after four tranfers.
Jawaban :
- Diketahui : KD = Caq /Cpent =5.0
Vm=Vs = 4 ml
Massa = 0,55 gram
- Jawab
𝐾𝐷 𝑥 𝑉𝑠 5𝑥4 20 5
p= = = =
𝐾𝐷 𝑥 𝑉𝑠 + 𝑉𝑚 5𝑥 4+ 4 24 6
 𝑉𝑚 4 1
q= = =
𝐾𝐷 𝑥 𝑉𝑠 + 𝑉𝑚 5𝑥 4+ 4 6
(p+q)n = p4 + 4p3q + 6a2b2 + 4pq3 + q4
5 4 5 3 1 1 5 2 1 2 5 1 1 3 1 4
= (6) +4(6) (6) + 6(6) (6) + 4 (6) (6) +(6)
625 125 25 5 1
= 1296 + 4 (1296)+ 6(1296)+4(1296)+(1296)
625 500 150 20 1
= 1296 + 1296 + 1296 + 1296 + 1296

the fraction of the compound which is in each vessel after four tranfers adalah 48,22%,
38,58%, 11,57%, 1,54%, dan 0,07%(0,1)%

3-7 Three extractions with 50 ml portions of chloroform removed 97% of a solute from 200
ml of an aquoes solution. Calculate the distribution coefficient of the solute. KD =
Cchlor/Caq
Jawaban :
- Diket : forg = 0,97
Vorg = 50 ml
Vaq = 200 ml
n =3
- Ditanya : KD?
- Jawab : faq = 1 - forg
= 1 - 0,97
= 0,03
𝑉𝑎𝑞
faq = ( )𝑛
𝑉𝑎𝑞 +𝐾𝐷 .𝑉𝑜𝑟𝑔

200
0,03 = ( )3
200+𝐾𝐷 .50

3 200
√0,03 = 200+𝐾
𝐷 .50

0,31(200 + 𝐾𝐷 . 50) = 200

62 + 15,5KD = 200
138
KD = 15,5

KD = 8,9
3-8 two weak base (organic amines) have basic dissociation constant of Kba = 1 x10-4 and KbB
= 1 x 10-8 . both bases have distribution coefficients approximately 10 beetween chloform
and water. Describe a procedure, making the use of the difference in Kb for seperating two
by extraction.
-
Diketahui : Kba = 1 x10-4
 KbB = 1 x 10-8
KD = 10 :
- Ditanya :
- Jawab :
Misal: pH = 8
𝐾𝑑 10
DA = 1+𝐾 −
= 1+(1 x10−4 /10−6 ) = 0,09901
𝑏𝐴 /[𝑂𝐻 ]

𝐾𝑑 10
DB = 1+𝐾 −]
= 1+(1 x10−8 /10−6 ) = 9,90099
𝑏𝐵 /[𝑂𝐻

3-9 Two weak acid, HX and HY, have distribution coefficient KD = Cet / Caq of 5 and 50,
respectively and dissociation constants of 1 x 10-4 and 1 x 10-8 . respectively. Calculate the
distribution ratios of two acid at integral values of pH of the aquoes solution from pH 4 to
1, assuming equal volumes of the two solvents. What is the minimum pH for which the
ratio of D values is at least 105 ?
Jawaban :
- Diket: KD Hx = Cet/ Caq = 5
KD HY = Cet/ Caq = 50
Ka Hx = 1 x 10-4
Ka HY = 1 x 10-8
V Hx = V HY
- Ditanya: D pH 4 sampai pH 11....?
- Jawab :
a. pH =4
[𝐻 + ] = 10-4
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−4 ]
5
=
1+1
5
=
2
= 2,5

b. pH =5
+
[𝐻 ] = 10-5
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
 5
=
10−4
1+
[10−5 ]
5
=
1 + 101
5
=
11
= 0,45

c. pH =6
+
[𝐻 ] = 10-6
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−6 ]
= 0,0495
d. pH =7
+
[𝐻 ] = 10-7
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]

= 0,004995
e. pH =8
+
[𝐻 ] = 10-8
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−8 ]
= 0,00049
f. pH =9
+
[𝐻 ] = 10-9
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−9 ]
= 0,000049
g. pH = 10
[𝐻 + ] = 10-10
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−10 ]
= 0,0000049
h. pH = 11
+
[𝐻 ] = 10-11
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
5
=
10−4
1+
[10−11 ]
= 0,0000049
i. pH =4
+
[𝐻 ] = 10-4
𝐾𝐷
D HY pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−4 ]
50
=
1 + 10−4
= 49,95
= 50
j. pH =5
+
[𝐻 ] = 10-5
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−5 ]
50
=
1 + 10−3
= 49,5

k. pH =6
+
[𝐻 ] = 10-6
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−6 ]
= 49,504
l. pH =7
+
[𝐻 ] = 10-7
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−7 ]
= 0,004995
m. pH =8
+
[𝐻 ] = 10-8
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−8 ]
= 25
n. pH =9
+
[𝐻 ] = 10-9
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−9 ]
= 4,45
o. pH = 10
+
[𝐻 ] = 10-10
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−10 ]
= 0,4950
p. pH = 11
+
[𝐻 ] = 10-11
𝐾𝐷
D Hx pH 4 = 𝐾𝑞
1+ +
[𝐻 ]
50
=
10−8
1+
[10−11 ]
= 0,0499
Tabel hasil perhitungan
pH DHx DHY
4 2,5 50
5 0,45 49,5
6 0,0495 49,504
7 0,004995 45,45
8 0,00049 25
9 0,000049 4,54
10 0,0000049 0,4950
11 0,00000049 0,0499
Jadi, pH minimal dengan nilai D > 10−5 adalah pH = 10
3-10 Formaldehyde has a distribution coefficient, Cet/Caq = 0,111 at 25oC. How many liters of
water will be required to remove in one extraction 95% of the formaldehyde from 1 liter
of ether containing 0,5 mole of formaldehyde ?
Jawaban:
- D1: f org= 0,95
f aq= 1-0,95= 0,05
V org= 1 L
KD= C org/ C aq= 0,111
n= 1
- D2: V air ...?
- D3:
𝑉 𝑎𝑞
faq= (𝑉 𝑎𝑞+𝐾𝐷.1𝐿)1

𝑉 𝑎𝑞
0,05= (𝑉 𝑎𝑞+1𝐿.𝐾𝐷)1

0,05 . Vaq + 0,111 . 0,05= V aq

0,00555= 0,95 Vaq

Vaq = 0,0058 L

= 5,8 mL

3-11 How much formaldehyde would remain in 50 ml of ether initially containing 5 gram of
formaldehyde after five succesive extractions with 25 ml portion of water ?
Jawaban :
- Diket: Vorg = 50 mL
Massa = 5 gram
n=5
Vaq = 25 mL
- Ditanya: forg = ...?
Dimisalkan D = 10
- Jawab:
𝑉 𝑎𝑞
faq = (𝑉 𝑎𝑞+𝐷 (𝑉𝑜𝑟𝑔))5 .Wo
25 𝑚𝐿
1 – forg = ( 25 𝑚𝐿+10 (50 𝑚𝐿))5 . 5 gram
1 – forg = 12.10-7
forg = 1 - 12.10-7
f0rg = 1 mg

3-12 Suppose you were given 100 mL of an aqueos solution containing 1 mL of LSD. You
wish to extract the LSD into ether.the distribution coefficient is given by
 Cet
KD =
= 10
Caq
a. How much LSD would be extracted with one 150 mL portion of ether?
b. How much LSD would be extracted with three successive 50 mL portion of ether?
Jawaban :
a. How much LSD would be extracted with one 150 mL portion of ether?
Vaq
faq =V . W0
aq +KD Vorg
100 mL
1 − forg = ( ) . 1 mg
100 mL + 10 . 150 mL
100 mL
forg =( ) . 1 mg
1600 mL
forg = 1 − 0,0625 mg
forg = 0,9375 mg

b. How much LSD would be extracted with one 150 mL portion of ether?
n
Vaq
faq = (V ) . W0
aq +KD Vorg
3
100 mL
1 − forg = ( ) . W0
100 mL + 10 . 50 mL
100 mL
1 − forg = ( ) . 1 mg
600 mL
1 − forg = ((0,167)3 )mg
forg = 1 − 0,0046 mg
forg = 0,995mg

3-13 the dissociation constant for propionic acid, HOP, in water is Ka =1 x10-5 You are given
and its distribution coefficient between ether and water is KD =2,85. You are given a
solution of 8 gram of HOPr in 500 ml of water which has been adjusted to pH 4 by the
addition off base. The HOPr is extacted from aqueuos solution with two 250 ml portion
of ether. What is the pH of the waterlayer affter the second extraction?
Jawaban:
- Diketahui : Asam Propionat
𝐾𝑎 = 1,00 × 10−3
𝐾𝐷 = 2,85
𝑤(𝑜) = 8,00 gr
𝑉(𝑎) = 500 mL
pH1 = 4 → [𝐻 + ] = 10−4 (suasana basa)
𝑉(𝑜) = 250 x 2 (2x ekstraksi)
- Ditanya : .............. pH2 ?
- Jawab :
𝐾
 D = 𝐷𝐾𝑎
1+ +
[𝐻 ]
 2,85
= 1×10−5
1+
10−4
=2,590
𝑉(𝑎)
 𝑤(𝑎) = 𝑤(𝑜) (𝐷𝑉 )𝑛
(𝑜) +𝑉(𝑎)
500
= 8(2,590(500)+500)2
500
= 8(1147,5)2
= 1,5189 𝑔𝑟
𝑚𝑎𝑠𝑠𝑎 1000
 M =𝑚𝑎𝑠𝑠𝑎 𝑚𝑜𝑙𝑎𝑟 × 𝑉 (𝑚𝐿)
1,1589 1000
= ×
18 2
=0,1688
 +
[𝐻 ] 2 =√𝐾𝑎 × 𝑀
= √1 × 10−5 (0,1688)
= 1,2990 × 10-3
 pH2 = 3 - log 1,2990
= 2,88635