KIMIA ANORGANIK LANJUT

Dr. Jumaeri, M.Si/

Dr. F. Widhi Mahatmanti
Pendidikan IPA S2 Program Pasca
Sarjana
Universitas Negeri
Semarang

1
 IDENTITAS MATA KULIAH
1. NAMA MATA KULIAH : KIMIA ANORGANIK LANJUT

2. CAPAIAN PEMBELAJARAN LULUSAN

CP Pengetahuan : Menguasai ilmu dasar lain yang
menunjang pemahaman ilmu kimia dan keterkaitannya sesuai
dengan perkembangan iptek.

3. CAPAIAN PEMBELAJARAN MATA KULIAH

Memahami secara seksama, teliti dan cermat dan mengerti secara komprehensif dan
bertanggungjawab tentang prinsip-prinsip reaksi kimia anorganik dan faktor-faktor
yang mempengaruhi, kestabilan termodinamika dan kinetika dalam reaksi anorganik,
teori koordinasi (teori ikatan kovalen, teori medan kristal dan teori orbaital molekul)
dan prinsip-prinsip reaksi koordinasi, kinetika dan adsorpsi padat-cair dalam
kaitannya dengan penanganan limbah industri menggunakan adsorben/katalis
berbasis konservasi.
4. DOSEN PENGAMPU : Dr. Jumaeri, M.Si/ Dr. F. Widhi Mahatmanti, S.Si., M.Si
 DAFTAR MATERI
PERTEMUAN MATERI POKOK SUMBER
1 Kontrak Perkuliahan
2 Prinsip-prinsip reaksi anorganik

3 Faktor-faktor yang mempengaruhi prinsip-prinsip

reaksi anorganik
4 Kestabilan secara termodinamika
5 Kelabilan secara kinetika
6 Teori ikatan valensi
7 Teori Medan Kristal
8 Teori Orbital Molekul
9 Adsorpsi padat-cair
10 Pengantar ke adsorben
11 Mekanisme adsorpsi padat-cair
12 Aplikasi katalis pada pengolahan limbah industri
13 Mekanisme kerja katalis pada aplikasi pengolahan
limbah industri
14 Review jurnal adsorpsi dan katalis
 THE SCOPE OF CHEMISTRY :

INORGANIC CHEMISTRY,
ORGANIC CHEMISTRY,
& BIOCHEMISTRY

PHYSICAL ANALYTICAL
CHEMISTRY CHEMISTRY

THEORETICAL DEVICES EXPERIMENTAL DEVICES

05/14/20 4
 Kornhauser (1981) :

 It is not chemistry if we learn theories

without facts, and it is not science if we
learn only facts without learning theories.

 Theories must not replace facts in

chemistry, but should explain them.

05/14/20 5
 CHEMICAL REACTION
is the focal point of any chemical
studies

05/14/20 6
 Why do chemical reactions occur?
The purpose of this chapter is to examine the nature of
chemical change.

Focusing on the recognizing all setting forth the basic

principles that help us to understand why chemical
reactions occur.

For the very essence of practical chemistry is the scientific

control of chemical change.

05/14/20 7
 If it is known why it occurs, then we can know what
conditions are necessary to cause or prevent its
occurrence, and we can direct our ingenuity toward
establishing such conditions.

Furthermore, such understanding should be invaluable to

students, who without it are faced with an almost infinite
variety of chemical equations to be memorized but with
110 basis for recognizing that they do make sense.

05/14/20 8
 Before we can consider "Why" reactions occur, it is
necessary to think of what happens during the
occurring of a chemical reaction.
reaction

Reactants  products
In order for this to happen, atoms, which are initially
attached to one another in a certain way in the
reactants, become separated, at least to some
extent, and rearranged in the products.

05/14/20 9
 E1 = mgh1

E2 = mgh2
05/14/20 10
 THE CONCEPT OF ENERGY
Definition

Energy could be defined as the capacity of a system to do

work

q
heat
SYSTEM

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 The First Law of Thermodynamics :
In ordinary processes, energy is conserved, it is
neither created nor destroyed

q
heat
SYSTEM
W
work

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 If heat q is added to a system and work w is done
by the system, the total amount of energy added to
the system, (q - w);
w) is not destroyed but is stored
within the system to increase the internal energy ∆U

q
heat
SYSTEM
W
∆U work

05/14/20 13
 THE INTERNAL ENERGY

∆U = q - w

∆Unuclear : nuclear binding energy MeV

∆Uelectronic : electronic energy Kcal/mole

∆Uvibration : vibration energy cal/mole

∆Urotation : rotation energy cal/mole

∆Utranslation : translation energy cal/mole

05/14/20 14
 ∆U : How to measure?
Considering that mechanical work w is equal to p∆V :

∆U = q - p ∆V

∆U = qv
measurable at constant volume

05/14/20 15
 Since most chemical processes proceed at
constant pressure rather than at constant volume,
it is more convenient to use other new definition
of internal energy called enthalpy : H = U + pV or
∆H = ∆U + p∆V

∆U + p ∆V = qp

∆H = qp
measurable at constant presure

05/14/20 16
  If enthalpy (or internal energy) is the driving
force of chemical processes, it is reasonable to
expect that all chemical processes should be
followed by a heat release (exothermic).
 In practice, however, although it is true that
most chemical processes are exothermic,
some endothermic (heat absorbed) chemical
processes do exist.
 It may be concluded, therefore, that enthalpy
(or internal energy) is NOT the driving force
of chemical processes

05/14/20 17
 The Second Law of Thermodynamics :

It is impossible to take heat from a body of uniform

temperature and convert it entirely into work
without causing a change in the thermodynamic
state of some other body.

It is impossible to have chemical processes,

working with a 100 % efficiency. Some waste
energy must also be released.

05/14/20 18
 THE CONCEPT OF FREE ENERGY

∆G = ∆H - T∆S

Free energy Enthalpy Waste

Energy

05/14/20 19
 ∆G = ∆H - T∆S

Chemical System
Bonding Structure

05/14/20 20
 CHEMICAL BONDING :
A Thermodynamic Interpretation

A B A B

05/14/20 21
 ATRACTIVE ENERGY :
• Between nucleus A and electron B
• Between electron A and nucleus B

Uatt= - Catt/r
REPULSIVE ENERGY :
• Between nucleus A and nucleus B
• Between electron A and electron B

Urep= + Crep/r
05/14/20 22
 U

Urep= + Crep/r

Uatt= - Catt/r

05/14/20 23
 BOND ENERGY :
The energy required to break down
chemical bond into separate atoms

BOND LENGTH :
The equilibrium distance between two
atoms involving chemical bond.

05/14/20 24
 BOND ENERGY vs INTERAL ENERGY

INTERNAL ENERGY U :
The most stable chemical bond would be
formed at the lowest internal energy

BOND ENERGY :
The stronger chemical bond would be
formed with bigger bond energy

05/14/20 25
 Chemical processes tend to proceed
spontaneously in the direction of diminished
free energy, i.e. when the free energy
change, G, is negative.

∆G is the driving force of

chemical processes

05/14/20 26
 Chemical processes tends to proceed
spontaneously only under one of the
following sets of conditions :
 If the total bonding forces in the products exceed
those in the reactants and the total disorder (entropy)
of the products is higher; or
 If the total bonding forces in the products exceed
those in the reactants and the total disorder in the
products is lower but not enough lower to make TS
greater than H; or
 the total bonding forces in the products are weaker
than those in the reactants but the entropy increase
(increase in disorder) is more than large enough to
compensate for the heat absorbed.
05/14/20 27
 A  B

GA > GB ΔG < 0 Spontaneous change : A  B

GA = GB ΔG = 0 A  B is at the equilibrium state

GA < GB ΔG > 0 Spontaneous change : B  A

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 CHEMICAL EQUILIBRIUM :
A Thermodynamic Interpretation

Gi = Gio + RT ln [i]

A  B ∆G = GB – GA

GA GB

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 A  B
GB = GBo + RT ln [B]
GA = GAo + RT ln [A]

∆G = ∆Go+ RT ln [B]/[A]

∆G = ∆Go+ RT ln Q
Q : reaction quotient

05/14/20 30
 A  B
At equilibrium state (∆G = 0) :

- ΔGo = RT ln K THEORETICAL
CONCEPT

K = [B]eq/[A]eq PRACTICAL
APPLICATION

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 A general chemical process :

aA+bB cC +dD

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

05/14/20 32
A. Electrolytic Dissociation of Water

H2O  H+ + OH-

Kw = [H+] [OH-]

05/14/20 33
Ion Product of Water Kw :

T, ºC Kw pKw

0 0.12 x 10-14 14.93

15 0.45 x 10-14 14. 35
20 0.68 x 10-14 14.17
25 1.01 x 10-14 14.00
30 1.47 x 10-14 13.83
50 5.48 x 10-14 13.26

05/14/20 34
B. Equilibrium of Acids and Bases :

HA  H3O+ + A-
Ka = [H+] x [A-]/[A]

B + H+  BH+ + OH-
Kb = [BH+] x [OH-]/[B]

05/14/20 35
Acidity and Bacisity Constant :
Acid pKa Base pKb
HClO4 -7 ClO4- 21
HCl -3 Cl- 17
HNO3 -1 NO3- 15
H30+ 0 H20 14
H2S 7.1 HS- 6.9
NH4+ 9.3 NH3 4.7
H2O 14 OH- 0
NH3 23 NH2 -9
OH- 24 O2- -10
05/14/20 36
 Ka is the experimental measure of
acid strength

Kb is the experimental measure of

base strength

05/14/20 37
 THE PRINCIPLES OF ENTROPY

05/14/20 38
 P, V, T P, V, T

05/14/20 39
 MORE ORDRED
LESS DISORDRED
LOW ENTROPY


LESS ORDERED
MORE
DISORDERED

HIGH ENTROPY
05/14/20 40
 STRONG LARGE LOW
LOW
 ENTHALPY
CHEMICAL
BONDS
~ BOND
~
ENERGY
INTERNAL
ENERGY

WEAK WEAK HIGH

CHEMICAL ~ BOND ~ INTERNAL  HIGH
BONDS ENERGY ENERGY ENTHALPY

05/14/20 41
 ∆G = ∆H - T ∆ S

System Structure

Chemical Bonding

05/14/20 42
Principle-1 :
Chemical processes tend to proceed spontaneously
in the direction of diminished free energy, i.e. when
the free energy change, G, is negative.

∆G = ∆H - T∆S is the driving force of

chemical processes

05/14/20 43
 Chemical processes tends to proceed spontaneously
only under one of the following sets of conditions :

 If the total bonding forces in the products exceed those

in the reactants and the total disorder (entropy) of the
products is higher; or
 If the total bonding forces in the products exceed those
in the reactants and the total disorder in the products
is lower but not enough lower to make TS greater
than H; or
 If the total bonding forces in the products are weaker
than those in the reactants but the entropy increase
(increase in disorder) is more than large enough to
compensate for the heat absorbed.

05/14/20 44
 ∆G = ∆H - T ∆ S

System Structure

Chemical Bonding

05/14/20 45
Chemical processes tends to proceed
spontaneously, if the total bonding forces in the
products exceed those in the reactants and the total
disorder (entropy) of the products is higher

∆H = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-SR) > 0 ∆G < 0

05/14/20 46
Chemical processes tends to proceed
spontaneously, If the total bonding forces in the
products exceed those in the reactants and the total
disorder in the products is lower but not enough
lower to make TS greater than H

∆H = (HP-HR) < 0

∆G = ∆H - T∆S

∆S = (SP-SR) < 0 ∆G < 0

05/14/20 47
Chemical processes tends to proceed
spontaneously, If the total bonding forces in the
products are weaker than those in the reactants but
the entropy increase (increase in disorder) is more
than large enough to compensate for the heat
absorbed.
∆H = (HP-HR) > 0

∆G = ∆H - T∆S

∆S = (SP-SR) > 0 ∆G < 0

05/14/20 48
 Principle-2 :
The gaseous state is more probable than
the liquid state, which in turn is more
probable than the solid state

SOLID  LIQUID  GAS

05/14/20 49
 Entropy of Various Substances at 25° (in eu)
Entropy Values at 25° (in eu)
Substance
Solid Liquid Gas

Sodium Na 12.30 13.83 36.71

Phosphorous P 9.82 10.28 38.98
Silicone Si 4.43 11.21 40.12
Lead Pb 15.50 17.14 41.89
Water H2O - 16.72 45.11
Methanol CH3OH - 30.30 56.80
Boron trioxide B2O3 12.91 18.55 64.42
Silicone dioxide SiO2 10.00 11.35 54.62
Lithium oxide Li2O 898 9.86 56.03
Beryllium oxide BeO 3.38 10.50 47.21
Titanium oxide TiO2 12.01 15.43 56.44
Lead oxide PbO 15.59 20.55 57.35
Boron trichloride BCl3 45.30 - 85.30
Silicone tetrachloride SiCl4 - 57.20 79.20
Lead chloride PbCl2 32.50 38.34 76.63
05/14/20
Sodium chloride NaCl 17.33 20.22 50
54.88
 Principle-3 :
A monatomic gas is more probable than a
polyatomic molecular gas, and hence
tends to have higher entropy

MOLECULAR STATE  ATOMIC STATE

05/14/20 51
 Entropy of Monatomic and Polyatomic Gas
(in eu/g atom)

H 27 .4 H2 15 6 - -
N 36.6 N2 22.9 - -
O 38.5 O2 24.5 O3 19.0
F 37.9 F2 24.4 - -
Si 40.1 Si2 17.5 - -
P 39.0 P2 26.1 P4 16.7
S 40.1 S2 27.3 S8 12.9
Cl 39.5 Cl2 26.6 - -
NO2 57 .5 N2O4 36.4 - -
05/14/20 52
 Principle-4 :
An amorphous solid is more probable than a
crystalline solid, and a simple crystalline solid
is more probable than a more complex
crystalline solid

CRYSTALLYNE  AMORPHOUS

05/14/20 53
 Principle-5 :
A molecular addition compound, or a
coordination complex, is less probable than
its separate components

H3N-BF3  NH3 + BF3

Cu(NH3)4SO4  Cu2++ 4NH3+ SO42-

05/14/20 54
 Principle-6 :
Compounds or elements of higher atomic
weight, or molecule of the free elements
themselves, tend to have higher entropy

05/14/20 55
 Principle-7 :
At ordinary temperatures, entropy effects are
commonly small enough to have relatively little
effects on the direction of reaction, unless the
difference in total bonding energy between
reactants and products is relatively small.

05/14/20 56
 Comparison on the values of Enthalpies and of Free
Energies of Formation (in kcal mole-1).
Substances Hfo Gfo T Sfo
H2O (l) - 57.80 - 54.64 + 3.16
HCl (g) - 22.00 - 22.77 - 0.77
SO2 (g) - 70.96 - 71.79 - 0.83
H2S (g) - 4.82 - 7.89 - 3.67
H2Te (g) + 36.90 + 33.10 - 3.80
KNO3 (c) - 117.16 - 93.96 + 23.20
Na2CO3 (c) - 270.30 - 250.40 + 19.90
Al2(SO4)3 (c) - 820.98 - 738.99 + 81.99
NH3 (g) - 11.04 - 3.98 + 7.06
N O4 (g)
05/14/20 2
+ 2.31 + 23.49 + 21.18 57
 Before the concept of entropy had been clearly
recognized, the heat of a reaction (entalpy) was
the sole factor determining the direction of
spontaneous reaction.

Entropy units are calories per degree per mole,

and the entropy changes accompanying reaction
are often only a few entropy units, whereas heats
of reaction are commonly more than a kilocalorie
per mole.

05/14/20 58
 Principle-8 :
All chemical reactions that increase
the entropy occur spontaneously at
high enough temperatures

05/14/20 59
 Energy T∆S = f (T)

∆H = f (T)

∆S = f (T)
∆G > 0

∆G < 0 T (K)
TC

05/14/20 60
∆G = ∆H - T ∆S
Comparison on the Values of Standard Enthalpies and
of Free Energies for Some Chemical Reactions

Hfo Gfo

Reactions kcal/mol kcal/mol

CCl4(g) + 2 H2O(g)  CO2 (g) + 4HCl(g) - 41.2 - 61.2

SF4 (g) + 3 H2O (g)  SO3 (g) + 6HF(g) - 45.0 - 75.9
CaO(c) + CO2(g)  CaCO3(c) - 42.5 - 31.1
CH4(g)+2 O2 (g)  CO2 (g)+ 2 H2O (g) - 191.8 - 191.4
AsCl3(l) +3 NaF(c)  3NaCl(c) + AsF3(g) - 24.7 - 31.7
AlBr3 (c) + PCl3 (g)  AlCl3(c) + PBr3 (g) - 3.1 - 4.3
CH3OH(l)+NH3(g) CH3NH2(g) + H2O(g) + 3.5 - 4.3
05/14/20 61