Kesetimbangan Kimia

dan Titrasi Asam Basa

Materi ke 2
1. Tetapan kesetimbangan
H2 (g) + I2 (g) 2HI (g)

Reversibel
Konsentrasi reaktan & produk konstan
seiring waktu berjalan
kesetimbangan
Tetapan kesetimbangan (K)

K =
2. Larutan berair
Elektrolit :
1. Lemah ( HOAc, HF, H2CO3, H2S)
2. Kuat (NaOH, KOH, HCl, HNO3,
HClO4, H2SO4)
Ketika elektrolit lemah menjadi ion =
tetapan disosiasi
 Air sbg amfoter, mengalami autoprotolisis :
AMFOTIR : Senyawa yg bisa bfungsi sbg
asam dan basa
Autoprotonasi dalam air

2H2O (l) H3O+ (aq) + OH- (aq)

K = [H3O+][OH-] = [H+][OH-]

K = tetapan ionisai air, Kw

[H+] = [OH-] = 1.0 x10-7 M

Kw = [H+][OH-]=(1.0 x 10-7 M)2 = 1.0 x 10-14 M
(suhu 250C)
3. Kesetimbangan asam basa

TEORI BRONSTED LOWRY

definisi lebih : luas daripada arrhenius

asam : donor proton
basa : akseptor proton
tidak hanya berlaku untuk larutan, tapi
bisa untuk molekul, ion, dan gas
Pasangan asam dan basa
konjugasi
DISOSIASI ASAM SECARA UMUM
Disosiasi asam :
HA + H2O H3O+ + A-

HA : asam
H2O : basa
H3O+ : asam rekonjugasi, dibentuk
dari basa setelah mendapatkan
proton
A- : basa terkonjugasi, dibentuk dari
asam setelah melepas proton
SIFAT ASAM
Berasa masam. Vinegar adl larutan
asam asetat.
Buah-buahan mengandung asam
sitrat.
Reaksi dengan logam tertentu
hasilkan gas hidrogen.
Reaksi dengan karbonat (-CO32-)dan
bikarbonat (HCO3-) menghasilkan gas
CO2
Kesetimbangan asam
HA + H2O H3O+ +
A-
Contoh :

HCl H+ + Cl-
CH3COOH H+ +
CH3COO-
NH4 H+ + NH3
C6H5NH3+ H+ + C6H5NH2
 ASAM KUAT DAN LEMAH
Contoh : HNO3, HCl, H2SO4,HClO4, HBr, HI, HBrO4
dan HIO4

Asam kuat terionisasi sempurna atau hampir

sempurna dlm air (100%)
 Asam Kuat dan Lemah
Asamlemah terionisasi kurang dari 100%
dalam air.
Contoh : Asam asetat = CH3CO2H
 Asam kuat mhasilkan basa terkonjugasi
yang lemah

asam lemah hasilkan basa terkonjugasi

yang kuat

Asam kuat : H2SO4, HCl, HNO3 DAN HClO4

Asam lemah : H3PO4, HNO2, HOCl, asam

organik
Kekuatan Asam Dan Basa
NAMA ASAM BASA
KONJUGAT
HClO4 ClO 4
HCl Cl -
H2SO4 HSO4-
HNO3 NO 3-
H 3 O+ H 2O
H2SO3 HSO 3-
H2SO4- SO 42-
H3PO4- H 2PO4-
HF F-
HC2H3O2 KEKUATAN C 2H302- KEKUATAN
H2CO3 MENURUN HCO 3- MENINGKAT
H2S HS-
Asam Monoprotik Dan Diprotik
Asam momoprotik : mdonor 1 proton
Contoh : HF, HCl, HNO3
Asam poliprotik : m;donor more one proton
Asam diprotik : m;donor 2 proton,
contoh : H2SO4.

H2SO4 + H2O HSO4- + H3O+

HSO4- + H2O SO42- + H3O+
Konstanta Kesetimbangan Pada
Asam Lemah

Ka asam lemah < 1

pH : 2 - 7
BASA
Arrhenius : Senyawa Yang Menghasilkan
Oh- Dalam Larutan
Bronsted-lowry : Aseptor Proton
Basa Kuat : Tdisosiasi Sempurna
Basa Lemah : Tdisosiasi Tak Sempurna

Contoh : Hidroksida Logam Alkali : Naoh

Dan Koh
Contoh Lain : Hidroksida Logam Alkali
Tanah
Antasida : Penghilang Asam Lambung
Konstanta Keseimbangan
Basa Lemah

Kb BASA LEMAH < 1

pH : 7 - 12
Konstanta Basa
basa sebagai aseptor proton
konstanta dissosiasi :

B (aq) + H2O (l) BH+(aq) + OH- (aq)

[BH+] [OH-]
Kb = ----------------
[B]
Contoh :
Hitung pH larutan NH3 15 M (Kb = 1.8 x 10-5)
Hubungan
Ka, Kb, [H3O]
dan pH
Titrasi dan kurva pH
Plotting pH suatu larutan dapat dianalisis sebagai
fungsi jumlah titran yang ditambahkan
Dari kurva titrasi-pH ditentukan titik equivalence
dimana titran yang ditambahkan cukup bereaksi
secara eksak dengan subtansi dalam larutan yang
dititrasi.
1. Titrasi asam kuat-basa kuat

Contoh :
Sebanyak 50,0 mL HNO3 0,2M
dititrasi dengan NaOH 0,1 M. Hitung
pH pada awal titrasi, setelah
penambahan 10, 50 dan 60 mL
titran.
Jawab
Kurva pH untuk titrasi 50.0 mL 0.200 M HNO3
dengan 0.100 M NaOH
2. Tirasi basa kuat-asam kuat
Contoh :
Sebanyak 100 mL NaOH 0,50 M
dititrasi dengan 0,10 M HCl. Hitung
pH pada awal titrasi, setelah
penambahan 10, 50 dan 60 mL
titran.
Jawab
The pH Curve for the Titration of 100.0 mL of
0.50 M NaOH with 1.0 M HCI
3. Kurva titrasi asam lemah-basa
kuat
Sebanyak 50,0 mL larutan 0,100 M
HB, Ka = 1,0 x10-5, dititrasi dengan
NaOH 0,1 M. Hitung pH pada awal
titrasi dan setelah penambahan 10,
50 dan 60 mL titran.
Jawab
Kurva pH untuk titrasi dari 50.0 mL 0.100 M
HC2H3O2 dengan 0.100 M NaOH
Kurva pH untuk
titrasi pada
beberapa sampel
asam 50.0-mL 0.10
M dgn berbagai
nilai Ka dgn 0.10
M NaOH
4. Titrasi basa lemah-asam kuat
Kurva pH untuk titrasi 100.0mL 0.050 M NH3
dgn 0.10 M HCl
Indikator asam basa

Suatu indikator adl suatu substansi yg

ditambahkan pada asam atau basa untuk
membuat titik akhir titrasi dgn perubh waarna.
Sbg contoh, phenolphthalein berubah dari tak
berwarna menjd pink pada titrasi asam dengan
basa.
Titik akhir titrasi harus berhubungan denagn
titik ekuivalen pd reaksi asam basa.
Warna indikator
Phenolphthalein
dalam suasana
asam dan basa
Indikator metil orange kuning pada larutan basa
dan merah pada larutan asam.
Suatu indikator asam/basa adalah asam
organik atau basa organik lemah yang bentuk
terdisosiasi berbeda warna dgn ketika tak
terdisosiasi,
HIn,

HIn + H2O In- + H3O+

warna asam warna basa

Kesetimbangan utk indikator basa : In, adalah

In + H2O InH+ + OH-

warna basa warna asam
Konstanta kesetimbangan

H 3 O I n
Ka + -
H In

H I n
H 3 O + K a
In
-
warna asam
H In 1 0

In 1

warna basa

H In 1

In 1 0
Pemilihan Indikator
1. Range pH untuk perub. Warna harus terjadi
diantara kenaikan garis vertikal secara
tegas/sharp atau (menurun tajam) pada kurva
titrasi.
2. Suatu indikator berubah warna pd range pH
= pKa 1, dimana pKa adlh keasaman dari
indikator yg digunakan.
Range pH untuk indikator
Indikator yang umum digunakan

Indicators: Acid Base pH Range Type of Titration

Color Color

1. Methyl orange Orange Yellow 3.2 4.5 strong acid-strong base

strong acid-weak base
2. Bromocresol Yellow Blue 3.8 5.4 strong acid-strong base
green strong acid-weak base
3. Methyl red Red Yellow 4.5 6.0 strong acid-strong base
strong acid-weak base
4. Bromothymol Yellow Blue 6.0 7.6 strong acid-strong base
blue
5. Phenol Red Orange Red 6.8 8.2 strong acid-strong base
weak acid-strong base

Useful pH Ranges for Several Common Indicators

 Buffers

SuatubufferdapatmempertahankanperubahanpH
ketikaterjadipenambahanataupengurangankeasaman
suatuasamlemah

RangeBuffer:rangepHdimanalarutanmasihmampu
mptahankanperubpHkarnapenambahanasamatau.
Range=+1pHdrpKaasamlemah
IfpKis4.8thebufferingrangeis3.8 5.8

Why?
Persamaan Henderson - Hasselbalch

Dari [ H ][ A ]
K
[ HA]

Rearange [ HA]
[H ] K
[A ]
[ A ]
pH log K log
[ HA]

[A ]
pH pK log
[ HA]
 -
[A ]
pH pK log
[HA]

[A ] 1 10
ratio varies from
[HA ] 10 1
Calculating the pH of solution during titration

Strong Acid-Strong Base Titration;

1. Net reaction: H3O+(aq) + OH-(aq) 2H2O
2. Determine the limiting reactant and calculate the
final concentration of H3O+ or OH- that is in excess.
3. Calculate pH using concentration of excess H3O+ or
OH-
Titration Problem: example #1

A 20.0 mL aliquot of 0.100 M HCl is titrated with

0.100 M NaOH solution. What is the pH of the
resulting solution after 15.0 mL of NaOH has been
added?

Reaction: H3O+(aq) + OH-(aq) 2H2O

[I]before rxn: 0.057 M 0.043 M
[C]from rxn: -0.043 M -0.043 M
[E]after rxn: 0.014 M 0.000

pH = -log(0.014) = 1.85
pH of Weak Acid-Strong Base Titrations

Net reaction: HA(aq) + OH-(aq) H2O + A-(aq);

1. Assume the reaction with OH- goes to completion;
2. If OH- is the limiting reactant:
(mol of HA)final = (mol of HA)initial (mol of OH-);
(mol of A-)final = (mol of OH-)
3. [HA]final = (mol of HA)final/Vfinal;
4. [A-]final = (mol A-)final/Vfinal
5. pH = pKa + log([A-]f/[HA]f)
Titration Problem: example #2

Weak Acid-Strong Base Titration:

A 20.0 mL aliquot of 0.100 M HNO2 is titrated with
0.100 M NaOH. (a) What is the pH of the solution
before titration? (b) What is the pH of the solution
after 15.0 mL of NaOH has been added? (c) What is
the pH of the solution at equivalent point (after 20.0
mL of 0.100 M NaOH is added)?
(Ka of HNO2 = 4.0 x 10-4)
Solution to Titration Problem: example #2

(a) Solving initial concentration of H3O+ by

approximation method:
[ H 3O ] [HNO 2 ] x K a (0.100 x 4.0 x 10 -4 0.0063 M

pH = -log(0.0063) = 2.20
Solution to Titration Problem: example #2

(b) Concentrations after 15.0 mL of NaOH is added:

Reaction: HNO2(aq) + OH-(aq) NO2-(aq) + H2O
[I]before rxn: 0.057 M 0.043 M 0.000
[C]from rxn: -0.043 M -0.043 M +0.043 M
[E]after rxn: 0.014 M 0.000 0.043 M

pH = pKa + log([NO2-]f/[HNO2]f)
= -log(4.0 x 10-4) + log(0.043/0.014)
= 3.40 + 0.49 = 3.89
Solution to Titration Problem: example #2

(c) Calculating pH at equivalent point:

Reaction: HNO2(aq) + OH-(aq) NO2-(aq) + H2O
[I]before rxn: 0.050 M 0.050 M 0.000
[C]from rxn: -0.050 M -0.050 M +0.050 M
[E]after rxn: 0.000 M 0.000 0.050 M

At equivalent point, [NO2-] = 0.050 M

Kb for NO2- = Kw/Ka = (1.0 x 10-14)/(4.0 x 10-4)
= 2.5 x 10-11
Solution to Titration Problem: example #2

(c) Calculating pH at equivalent point (continue):

Set up the following equilibrium for the reaction of
NO2- with water:
Reaction: NO2-(aq) + H2O HNO2 + OH-(aq);
[I]before rxn: 0.050 M 0.000 0.000
[C]from rxn: -x +x +x
[E]after rxn: (0.050 x) x x
Solution to Titration Problem: example #2

(c) Calculating pH at equivalent point

(continue):

Kb = x2/(0.050 x) = 2.5 x 10-11

x = [OH-],
Using
approximation method, -11
[OH ] [NO 2 ] x K b (0.050 x 2.5 x 10
-
1.1 x 10 -6 M

pOH = -log(1.1 x 10-11) = 5.95

pH = 14.00 5.95 = 8.05
pH of Strong Acid-Weak Base Titrations

Net reaction: B(aq) + H3O+(aq) BH+(aq) + H2O;

1. Assume the reaction with H3O+ goes to completion;
2. If H3O+ is the limiting reactant, at the end of the
reaction, (mol B)final = (mol B)initial (mol H3O+);
3. (mol BH+)final = (mol H3O+)
4. [B]final = (mol B)final/Vfinal;
5. [BH+]final = (mol BH+)final/Vfinal
6. pH = pKa + log([B]f/[BH+]f; (pKa is for BH+)
Titration Problem: example #3

Strong Acid-Weak Base Titration:

A 20.0 mL aliquot of 0.100 M NH3 is titrated with
0.100 M HCl. (a) What is the pH of the solution
before titration? (b) What is the pH of the solution
after 10.0 mL of HCl has been added? (c) What is the
pH of the solution at equivalent point (after 20.0 mL
of 0.100 M HCl is added)?
(Kb of NH3 = 1.8 x 10-5)
Solution to Titration Problem: example #3

(a) Solving initial concentration of OH- by

approximation method:
[OH - ] [ NH 3 ] x K b
(0.100 x 1.8 x 10 -5 ) 1.3 x 10 -3 M
[H3O+] = Kw/[OH-] = (1.0 x 10-14)/(1.3 x 10-3)
= 7.5 x 10-12 M
pH = -log(7.5 x 10-12 M) = 11.13
Solution to Titration Problem: example #3

(b) Concentration after 10.0 mL of HCl is added:

Reaction: NH3(aq) + H3O+(aq) NH4+(aq) + H2O
[I]before rxn: 0.067 M 0.033 M 0.000
[C]from rxn: -0.033 M -0.033 M +0.033 M
[E]after rxn: 0.034 M 0.000 0.033 M

pH = pKa + log([NH3]f/[NH4+]f)
= -log(5.6 x 10-10) + log(0.034/0.033)
= 9.25 + (0.0) = 9.25
Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point:

Reaction: NH3(aq) + H3O+(aq) NH4+(aq) + H2O
[I]before rxn: 0.050 M 0.050 M 0.000
[C]from rxn: -0.050 M -0.050 M +0.050 M
[E]after rxn: 0.000 M 0.000 0.050 M

At equivalent point, [NH4+] = 0.050 M

Ka for NH4+ = Kw/Kb = (1.0 x 10-14)/(1.8 x 10-5)
= 5.6 x 10-10
Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point (continue):

Set up the following equilibrium for the reaction of
NO2- with water:

Reaction: NH3(aq) + H3O+(aq) NH4+(aq) + H2O

[I]before rxn: 0.050 M 0.000 0.000
[C]from rxn: -x +x +x
[E]after rxn: (0.050 x) x x
Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point (continue):

Ka = x2/(0.050 x) = 5.6 x 10-10

x = [H3O+],
Using approximation method,
[H 3O ] [NH 4 ] x K a
(0.050 x (5.6 x 10 -10 ) 5.3 x 10 -6 M
pH = -log(5.3 x 10-6 = 5.28
Titration Exercise #1

25.0 mL of 0.10 M HCl is titrated with 0.10 M NaOH

solution. (a) What is the pH of the acid before NaOH
solution is added? (b) What is the pH after 15.0 mL of
NaOH solution is added? (c) What is the pH of the
solution after 25.0 mL of NaOH is added?

(Answer: (a) pH = 1.00; (b) pH = 1.60; (c) pH = 7.00)

 Titration Exercise #2

25.0 mL of 0.10 M acetic acid is titrated with 0.10 M

NaOH solution. (a) What is the pH of the acid
solution before NaOH is added? (b) What is the pH
after 15.0 mL of NaOH solution is added? (c) What is
the pH after 25.0 mL of NaOH is added?

(Answer: (a) pH = 2.87; (b) pH = 4.92; pH = 8.72)

 Titration Exercise #3

25.0 mL of 0.10 M lactic acid, HC3H5O3, is titrated

with 0.10 M NaOH solution. After 15.0 mL of NaOH
is added, the solution has pH = 4.03. (a) Calculate the
Ka of lactic acid. (b) What is the initial pH of 0.10 M
lactic acid before NaOH is added?

(Answer: (a) Ka = 1.4 x 10-4; (b) pH = 2.43)