Materi I:

Pengantar Prinsip-prinsip Reaksi Kimia

Reaksi Kimia
 THE SCOPE OF CHEMISTRY :

INORGANIC CHEMISTRY,
ORGANIC CHEMISTRY,
& BIOCHEMISTRY

PHYSICAL ANALYTICAL
CHEMISTRY CHEMISTRY

THEORETICAL DEVICES
12/12/2017 EXPERIMENTAL DEVICES 2
 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.

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 CHEMICAL REACTION
is the focal point of any chemical
studies

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 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.

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 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.

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 Before we can consider "Why" reactions occur, it is
necessary to think of what happens during the
occurring of a chemical 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.

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 E1 = mgh1

E2 = mgh2
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 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); is not destroyed but is stored
within the system to increase the internal energy U

q
heat
SYSTEM
W
U work

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 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

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 U : How to measure?
Considering that mechanical work w is equal to pV :

U = q - p V

U = qv
measurable at constant volume

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 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 + pV

U + p V = qp

H = qp
measurable at constant presure

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 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

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 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.

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 THE CONCEPT OF FREE ENERGY

G = H - TS

Free energy Enthalpy Waste

Energy

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 G = H - TS

Chemical System
Bonding Structure

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 CHEMICAL BONDING :
A Thermodynamic Interpretation

A B A B

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 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
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 U

Urep= + Crep/r

Uatt= - Catt/r

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 BOND ENERGY :
The energy required to break down
chemical bond into separate atoms

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

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 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

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 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

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 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 TS
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.
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 A B

GA > GB G < 0 Spontaneous change : A B

GA = GB G = 0 A B is at the equilibrium state

GA < GB G > 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

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 A B
At equilibrium state (G = 0) :

- Go = 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

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A. Electrolytic Dissociation of Water

H2O H+ + OH-

Kw = [H+] [OH-]

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Ion Product of Water Kw :

T, C 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

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B. Equilibrium of Acids and Bases :

HA H3O+ + A-
Ka = [H+] x [A-]/[A]

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

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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
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 Ka is the experimental measure of
acid strength

Kb is the experimental measure of

base strength

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