KIMIA DASAR II

Dra. Bakti Mulyani, MSi.

 MATERI PERKULIAHAN
• KESETIMBANGAN KIMIA
• LARUTAN DAN SIFAT KOLIGATIF LARUTAN
• KESETIMBANGAN ASAM DAN BASA
• KELARUTAN DAN HASIL KALI KELARUTAN
• ELEKTROKIMIA
• RADIOKIMIA
• KOLOID
• KIMIA UNSUR
 Buku Acuan
• Brady, J.E. and G. E. Humiston. General
Chemistry. Principles and Structure. John
Wiley and Sons. Singapore.
• Keenan, W. and Kleinfelter. Kimia untuk
Universitas. (Alih bahasa oleh Hadiyana
Pujaatmaka). Penerbit Erlangga. Jakarta.
• General Chemistry/Fundamental
Chemistry/ Buku-buku Kimia Dasar yang
lain
CHEMICAL EQUILIBRIUM
 KESETIMBANGAN KIMIA
• KEADAAN KESETIMBANGAN
• HUKUM DAN TETAPAN
KESETIMBANGAN
• KESETIMBANGAN HOMOGEN DAN
HETEROGEN
• FAKTOR YANG MEMPENGARUHI
KESETIMBANGAN ( ASAS LE
CHATELIER )
• STOIKIO KESETIMBANGAN
 A. KEADAAN KESETIMBANGAN
• Fakta menunjukkan bahwa banyak reaksi yang
dapat berlangsung secara reversibel atau bolak
balik.
aA + bB  cC + Dd
• Suatu reaksi kimia dimana kecepatan
terbentuknya produk sama dengan
kecepatan terbentuknya kembali reaktan
dikatakan reaksi tersebut dalam keadaan
setimbang.
• Kesetimbangan bersifat dinamis.
Kesetimbangan Kimia
(C ) c ( D) d
K C
( A) a ( B ) b

HUKUM KESETIMBANGAN DAN

TETAPAN KESETIMBANGAN
• Harga tetapan kesetimbangan suatu reaksi
kimia ditentukan dari hasil percobaan
• Berdasarkan data percobaan tersebut dapat
disimpulkan bahwa pada reaksi
kesetimbangan yang berlangsung pada suhu
tetap hasil kali konsentrasi produk pangkat
koefisien reaksi dibagi dengan hasil kali
reaktan pangkat koefisien reaksi mempunyai
harga yang tetap.
 Equilibrium
I. Dynamic Equilibrium
II. Equilibrium Constant; Kc and Kp
III. Homogenous vs. Heterogeneous
Equilibrium
IV. Calculation of K from Equilibrium
Concentrations
 Equilibrium
I. Predicting Reaction Direction for
Nonequilibria Mixtures
• Reaction Quotient, Q
II. Le Chatlier’s Principle
III. Calculating Equilibrium Concentrations
from Initial Concentrations and K
• Square Root
• Quadratic Formula
Equilibrium is a state in which there are no observable
changes as time goes by.

Chemical equilibrium is achieved when:

• the rates of the forward and reverse reactions are equal and
they are not zero.
• the concentrations of the reactants and products remain
constant
Chemical equilibrium

N2O4 (g) 2NO2 (g)

14.1
 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

Equilibrium favors the reactant side

14.1
constant

14.1
 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K=
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

14.1
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.

N2O4 (g) 2NO2 (g)

[NO2] 2 PNO
2
2
Kc = Kp =
[N2O4] PN O
2 4

In most cases
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)n

n = moles of gaseous products – moles of gaseous reactants

= (c + d) – (a + b)
14.2
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

K‘c =
[CaCO3] [CaO] = constant

[CaCO3]
Kc = [CO2] = K‘c x Kp = PCO2
[CaO]

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.

14.2
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

14.2
 Ways Different States of Matter
Can Appear in the Equilibrium
Constant, K
Molarity Partial Pressure

gas, (g) YES YES

aqueous, (aq) YES ---

liquid, (l) --- ---

solid, (s) --- ---

 Writing Equilibrium Constant Expressions

• The concentrations of the reacting species in the

condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
• The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
• The equilibrium constant is a dimensionless quantity.
• In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.

14.2
 The equilibrium concentrations for the reaction between
carbon monoxide and molecular chlorine to form COCl2 (g)
at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)n

n = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

14.2
The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if
the PNO 2= 0.400 atm and PNO = 0.270 atm?

2
PNO PO 2
Kp = 2
PNO 2

2
PNO
PO2 = Kp 2
2
PNO

PO2 = 158 x (0.400)2/(0.270)2 = 347 atm

14.2
 Predicting Reaction Direction
from a Nonequilibrium Mixture

• Calculate Reaction Quotient, Q

• The expression for Q is the same as K
BUT nonequilibrium concentrations
rather than equilibrium concentrations
are put into the expression
• Compare the value of Q to K.
 The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

14.4
 Le Châtelier’s Principle

1. System starts at equilibrium.

2. A change/stress is then made to system
at equilibrium.
• Change in concentration
• Change in volume
• Change in pressure
• Change in Temperature
• Add Catalyst
3. System responds by shifting to reactant
or product side to restore equilibrium.
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.

• Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium
Add
shifts left to
NH3
offset stress

14.5
 Le Châtelier’s Principle

• Changes in Concentration continued

Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
14.5
Le Chatlier’s Principle

Removing SO2, O2
Le Chatlier’s Principle (cont)
Le Chatlier’s Principle (cont)
Le Chatlier’s Principle (cont)
 Le Châtelier’s Principle

• Changes in Volume and Pressure

(Only a factor with gases)

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

14.5
Le Châtelier’s Principle

Chemistry; The Science

in Context;by Thomas
R. Gilbert, Rein V.
Kirss, and Geoffrey
Davies, Norton
Publisher, 2004, p 752
 Le Châtelier’s Principle

• Changes in Temperature
Only factor that can change value of K

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

14.5
Le Châtelier’s Principle; Temperature Effect

Chemistry; The Science

in Context;by Thomas
R. Gilbert, Rein V.
Kirss, and Geoffrey
Davies, Norton
Publisher, 2004, p 764
 Le Châtelier’s Principle

• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
 uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.

14.5
 Le Châtelier’s Principle

Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no

Animation of Le Chatelier’s Principle

14.5
 Calculating Equilibrium Concentrations
from K and Initial Concentrations

1. Balance chemical equation.

2. Determine Q to see which way reaction will proceed to get
to equilibrium
3. Define changes needed to get to equilibrium. Use ‘x’ to
represent the change in concentration to get to equilibrium.
Determine expression for equilibrium concentration.
4. Write the expression for equilibrium constant, K.
5. Substitute expressions defined in step 3 into the equilibrium
constant (step 4).
6. Solve for x and plug value back to table made in step 3.
14.4
 At 12800C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g)

Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M

and [Br] = 0.012 M, calculate the concentrations of these
species at equilibrium.
Let x be the change in concentration of Br2
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2 Solve for x

Kc = Kc = = 1.1 x 10-3
[Br2] 0.063 - x
14.4
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
ax2 + bx + c =0 x=
-b ±  b 2
– 4ac
2a
x = -0.0105 x = -0.00178
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.0648 M
14.4
 2 SO2(g) + O2(g) 2 SO3(g)

• Perhatikan sistem kesetimbangan

homogen di atas :
Jika dimulai dengan SO3(g) murni dalam
bejana, ternyata pemanasan pada 727oC
pada tekanan 300 atm menghasilkan
suatu campuran kesetimbangan di mana
tekanan SO3(g) sebesar 76,9 % dari
tekanan total. Tentukan harga Kp.
N2O4 (g,red)  2NO2 (g,colorless)

• Sample problem:
– Consider a mixture of N2O4 and NO2 at a
total pressure of 1.5 atm… resulting from the
dissociation of N2O4.
• If Kp = 0.14 at the temperature of the experiment,
what fraction of the N2O4 originally present
dissociated?
– What happens if PT falls to 1.0 atm?
 NH4HS(s)  NH3(g) + H2S(g)

• If Kp = 0.11 at the temperature of the

experiment, what is the the partial
pressure of NH3? Of H2S?
• Add solid NH4HS into a reactor containing
0.50 atm of NH3 and calculate the partial
pressures of both gases at equilibrium.
Change in Free Energy

o
G G  RT ln(Q)
aA  bB  cC  dD
C  D 
Q a b
c d

 A B 
 Equilibrium Constant
• At equilibrium, Q =K.
Q
C  D 
c d
K
 A B 
a b

Useful equation in solving for unknown equilibrium

constants as long as reaction temp., stoichiometry,
and values for are known.
 G 0
K exp
RT
 Free Energi & Its Relationship to
Equilibrium Constant
• Equilibrium-state or position with minimum
possible free energy (change in free energy is
zero at equilibrium)

0
G 0 G  RT ln K
0
G  RT ln K
R = 8,314 J mol-1 K-1
 Soal latihan
1.Energi bebas pembentukan standar, ∆Gof dari
NO2(g) dan N2O4(g) pada suhu 25oC adalah
masing-masing 51,30 dan 97,82 kJ mol-1
Hitunglah Kp untuk kesetimbangan
N2O4(g) 2NO2(g)
pada suhu 25oC dan tekanan 1 atm.

2. Pada suhu 25oC dan tekanan total 0,298 atm,

tekanan parsial N2O4(g) adalah 0,15 atm.
Hitunglah harga Kp dan ∆Gof untuk perubahan
2 mol NO2(g) menjadi N2O4(g)
 4 rules to determine what value to use for
the concentrations in Q
• Rule 1: Solvents (e.g. water): [i] is equal to the
mole fraction of the solvent. Thus, [H 2O] always
equals 1.
• Rule 2: Pure solids in equilibrium with a solution
(e.g. CaCO3(s), Fe(OH)3(s)): [i] always equals 1.
• Rule 3:Gases in equilibrium with a solution (e.g.
CO2(g), O2(g)): [i] equals the partial pressure of
the gas (atm)
• Rule 4: Compounds dissolved in water: [i] is
always reported in units of moles/liter (molar).
 Equilibrium Constant
• At equilibrium, Q =K.

Q
C  D 
c d
K
 A B 
a b

• Useful equation in solving for unknown

equilibrium constants as long as reaction temp.,
stoichiometry, and values for ∆Gof are known.
0
 G
K exp
RT
 Effect of temperature on the
Equilibrium Constant
• Most tabulated equilibrium constants are
recorded at 25oC.
• Van’t Hoff relationship is used to convert
equilibrium constants to temperatures other than
those tabulated.

0
d ln K H
 2
dT RT
 Effect of temperature on the
Equilibrium Constant
• Most temperatures encountered in environmental
problems are relatively small.
• Therefore, temp differences are not that large. If
is assumed constant over the temp range.
K 2 H 0  1 1 
ln     Persamaan van’t Hoff
K1 R  T1 T2 
• This equation can be used to calculate an
equilibrium constant for any temp if the constant
is known at another absolute temp
 Aplikasi Kesetimbangan Kimia

• demineralisasi remineralisasi
• Proses demineralisasi dan remineralisasi
Ca5 (PO4)3OH(s) yang terdapat pada email gigi
merupakan salah satu contoh penggunaan hukum
de Chatelier.

Ca5 (PO4)3OH(s) 5Ca2+(aq) + 3PO43- (aq) + OH-(aq)

• Pada gigi yang sehat terdapat kesetimbangan
zat seperti di atas, tetapi apabila gigi
mengabsorbsi dan gula mengalami fermentasi,
maka kesetimbangan akan terganggu karena H +
akan beraksi dengan OH- membentuk H2O dan
ion PO43- akan menyebabkan HPO42-
• Berkurangnya ion OH- dan ion PO43- akan
menyebabkan Ca5(PO4)3OH yang larut lebih
banyak, sehingga gigi menjadi rusak. Fluorida
dapat mencegah kerusakan gigi karena dapat
menggantikan OH- dalam Ca5(PO4)3OH
terbentuknya Ca5(PO4)3F, sangat resisten
terhadap asam.