BLENT ECEVT UNIVERSITY

FACULTY OF ARTS AND SCIENCES

DEPARTMENT OF CHEMISTRY

CHM 193 GENERAL CHEMISTRY

PROF.DR.TRKAN KOPA

CHM 193-COURSE CONTENT

1. INTRODUCTION
2. ATOMS AND ATOMIC STRUCTURE
3. PERIODICAL TABLE
4. CHEMICAL BONDING
5. CHEMICAL CALCULATIONS
6. GASES
7. LIQUIDS
8. SOLUTIONS
9. CHEMICAL KINETICS
10. CHEMICAL EQUILIBRIUM
11. CHEMICAL THERMODYNAMICS
12. ELECTROCHEMISTRY

REFERENCES:
1. RALPH H.PETRUCCI, GENERAL CHEMISTRY, 5TH ED.,
MACMILLAN PUBLISHING, 1989.
2. CHARLES E. MORTIMER,
D.VAN NOSTRAND COMP.

CHEMISTRY,

4TH

ED.,

3. R. W. PARRY, H. BASCOW, P. MERRILL, CHEMISTRY,

4TH ED., PRENTICE-HALL, 1987.
4. ENDER
ERDK,
YKSEL
SARIKAYA,
TEMEL
NVERSTE KMYASI, GAZ KTABEV, 19.BASKI

EXAMS:

MID TERM EXAM (% 40)

FINAL (% 60)

1. INTRODUCTION
Chemistry: the science that is concerned with the
charactarization, composition, and transformations of matter.
BRANCHES OF CHEMISTY
INORGANIC CHEMISTRY
ORGANIC CHEMISTRY
ANALYTICAL CHEMISTRY
PHYSICAL CHEMISTRY
BIOCHEMISTRY
Inorganic Chemistry: deals with structures and reactions of nonmetals, metals.
Organic Chemistry: concerns with structures and reactions of
organic compounds.
Analytical Chemistry: concerns with the determination of chemical
compounds, their quantities
Physical Chemistry: investigation of the effects of various
physical parameters (temperature, pressure, concentration, etc.)
on matter and chemical reactions.
Application of physical methods to CHEMISTRY (between physics
and chemistry):
THERMODYNAMICS
ELECTROCHEMISTRY
CHEMICAL KINETICS
POLYMER CHEMISTRY
NUCLEOUS CHEMISTRY
QUANTUM CHEMISTRY
SPECTROSKOPY
STATISTICAL THERMODYNAMICS
CHEMICAL ENGINEERING
Biochemistry: chemistry in living organisms. Proteins, nucleic
acids are biopolymers composed of organic molecules.
Bioanalytical chemistry
Bioinorganic chemistry

Bioorganic chemistry
Theoretical chemistry: without any experimentation, based on
calculations
Chemical Engineering: processes and operations in industrial
scale, design for chemical tecnologies.
Biotechnology: progress related with biochemistry, biology,
medicine pharmacy; production of pharmaceuticals, gene therapy,
industrial scale production of pharmaceuticals.

The other brances of sciences related with chemistry

Metallurgy
Petroleum Engineering
Agrochemistry
Food chemistry
Food Engineering
Environmental chemistry Environmental Engineering
Textyl chemistry Textyl Engineering
Materials chemistry Materials Engineering
Pharmaceutical Materials
Medicinal chemistry
Chemoteraphy

UNITS
International System of Units (Systeme International dUnites-SI)
(1960, 11th General Conference of Weights and Measurements)
Base units and supplementary units of the International System of
Units (SI)
Base units

Measurement
length

Unit
meter

Symbol
M

mass

kilogram

Kg

time

second

electric current

ampere

Amp

temperature

kelvin

amount
substance

Supplementary
units

Mol

luminous
intensity

candela

cd

plane angle

radian

rad

solid angle

steradian

sr

Derived Units
Measurement

SI Unit

velocity

m/s

acceleration

m/s2

force

Surface area

m2

volume

m3

volumetric

of mole

flow m3/s

rate
Mass flow rate

kg/s

pressure

Pa (1 bar=105Pa)

density

kg/ m3

Energy

power

Viscosity

kg/m.s

Unit
1 A (Angstrm)
1 m (mikrometre)
1 in
1 ft

SI equivalent units
10-10 m
10-6 m
0.0254 m
0.3048 m

Area

1
1
1
1

102 m2
104 m2
6.452 10-4 m2
0.0929 m2

Mass

1 lb

0.4536 kg

Volume

1 litre
1 Gallon (US)
1 Gallon (imp)

10-3 m3
3.785 10-3 m3
4.546 10-3 m3

Force

1 kp (kilopound)
1 dyn
1lbf

9.81 N
10-5 N
4.448 N

Pressure

1
1
1
1
1
1

1.01325 x 105 Pa
0.98066 x 105 Pa
105 Pa
133.0 Pa
98.1 Pa
6891 Pa

Energy

1 cal
1 cal

Length

a (Ar)
ha (Hectar)
in2
ft2

atm
at
bar
torr (mmHg)
cm water
psi

4.184 J
4.1868 J

1 kw-hour
1 BTU
1 ft.lbf

3600 kJ
1.055 kJ
1.356 kJ

Power

1 BG (metric)
1 hP (ngiliz)

736 W
746 W

Temperature

1 C (difference)
-273.15 C

1K
0K

Viscosity

1 p (poise)
1 St (Stoke)
1 lb/ft.s

0.1 Pa.s
10-4 m2/s
1.488 kg/m.s

Heat conduction
surface film
coefficient

1 kcal/m.hour. C
1 kcal/cm.s. C
1 BTU/ft. hour. F

1.163 W/m.K
418.7 W/m.K
1.73 W/m.K

Cooling capacity

1 ton

3.52 kW

Derived Units
Force
F = ma

(Newton)

1 Newton:
1 N = 1 kg. 1 ms-2 = 1 kg m s-2
F = mg = 1 kg (9.81 ms-2) = 9.81 N
Pressure
P=F/A

(Pascal)

1 Pascal:
1 Pa = 1 N / 1 m2 = 1 N m
103 Pa = 1 kPa
106 Pa = 1 MPa

-2

1 bar = 105 N m

-2

= 105 Pa

1 bar = 102 kPa

1 bar = 0.1 MPa
P=F/A
Using mass of liquid
m=V
P=V/A

= hA/A

P=h

Example: Express 1 mmHg pressure in Pascal units,

P=h
P = 0.1 cm (13.6 g /cm3) = 1.36 g /cm2
P = 1.36 g /cm2 . (1 kg / 103 g ). (104 cm2 / 1m2 ). (9.81 N /1 kg )
P = 133.4 N / m2
1 mmHg (1 torr) = 133.4 Pa
1 atm = 76.0 cm (13.6 g /cm3)
1 atm = 1.0336 kg/ cm2 (at)
1 atm = 1.0336 (9.81) 104 = 1.013 105 N / m2
1 atm = 1.013 105 Pa
1 atm = 1.013 102 kPa

1 atm = 0.1013 MPa

1 at = 1.0 kg/cm2 (9.81 m/s2) = 9.81 N/cm2
1 at = 9.81 N/cm2 (10000 cm2 / 1 m2) = 98.1 kPa
1 psi = 1 lbf / 1in2 = 0.454 kg /(2.54)2 = 0.0703 at
1 psi = 0.0703 at (98.1 kPa/ 1 at) = 6.996 kPa

PROPERTIES OF MATTER:
Matter is any object or material that occupies space.
The quantity of matter is measured by its mass.
The characteristics that we can use to identify samples of
matter and distinguish them from one another are called
properties.
Extensive properties (capacity properties): depend on
quantity of matter:
mass, volume
Intensive

properties:

independent

of

quantity

of

matter:
density, melting point, boiling point
Density: is the ratio of the mass of an object or material to its
volume.
d= mass / volume
We can group properties into two broad categories:
Physical properties: a process in which an object
changes its physical apparence but not its basic composition is
called a physical change
Extensive properties + Intensive properties

Chemical properties: paper burns, iron rusts, wood rots.

In each case the object changes not only in physical apparence but
also in its basic composition.
In a chemical change, a sample of matter is transformed into
completely different materials.
reactivity of matter
Example: reactivity of sodium towards water
States of matter:
Solid
Liquid
Gas
Plasma (4th state of matter): at very high temperatures mixture of
atoms, molecules, ions and electrons (in space)
Homogeneous matter: consisting of one phase
solid, liquid, gas
copper, salt, NaCl solution, air, iron, nickel
alloy Heterogeneous matter: consisting of more than one phase
Composition is not constant, a mixture
Each phase carries own property
Pure matter: element or compound.
Element:
a substance comprised of just a single type of atom. Elements
cannot be decomposed into simpler substances, not by heating,
crushing, exposure to acids.
H, O, F,C, Cl
Compound:
Atoms of different elements can combine with one another to form
more complex substances called chemical compounds.
H2O, SO2

Synthesis: preparation
compounds.

of

compounds

from

elements

or

Analysis: determination
compounds

of

the

content

or

the

structure

of

BASIC LAWS OF CHEMISTY

LAW OF CONSERVATION OF MASS
Lomonossov
Lavoisier
Londolt
Etvos

1752
1774
1908
1909

MATTER CAN NEITHER BE CREATED NOR DESTROYED. Matter is

conserved during chemical reactions.
According to this law, mass balance can be written for every
chemical reaction.

LAW OF CONSTANT COMPOSITION

(LAW OF DEFINITE PROPORTIONS)
All samples of a given compound have the same composition, that
is, the same proportions by mass of the constituent elements.
Proust

1799

Simple Formula of chemical compounds

DALTONS ATOMIC THEORY

Each chemical element is composed of minute, indestructible

particles called atoms. Atoms can be neither created nor
destroyed during a chemical change.

All atoms of an element are alike in mass and other

properties, but the atoms of one element are different from
those of all other elemnents.

In chemical compounds, atoms of different elements combine

in simple numerical ratios: for example, one atom of A to one
of B (AB), one atom of A to two of B (AB2).

LAW OF MULTIPLE PROPORTIONS

If two elements form more than a single compound, the masses of
one element combined with a fixed mass of the second are in the
ratio of small whole numbers.
John Dalton

1803

GAY-LUSSAC, HUMBOLDT AND AVOGADRO LAWS

Proposed by :Joseph Louis Gay Lussac
1178-1850
Alexander von Humboldt 1769-1859
Developed by: Amedeo Avogadro
1811
H2, O2, Cl2, N2, HCl, NH3, CO2

Lomonossov
Lavoisier
Londolt
Etvos

1752
1774
1908
1909

DALTON ATOM KURAMI

J.Dalton modern kimyann en nemli kurucularndan biri.
Madde iin atom kuramn nermitir.
Dalton Kuram ktlenin korunumu ve sabit oranlar yasalarna ve
Dier gzlemlere dayanlarak nerilmitir.
1. madde, grnmeyen ve atom denilen paracklardan
olumutur.

2. bir elementin btn atomlar ayn zellikleri tar ve

dier bir elementin elliklerinden farkldr.
3. kimyasal reaksiyonlar, atomlarn dzenlenme trnn,
birleme eklinin deimesinden ibarettir.
Dalton Kuram, gzlemleri ve yasalar baaryla
aklamaktadr (Ktlenin korunumu ve sabit oranlar
yasalar). Katl oranlar yasas da ortaya kmaktadr.

2. ATOMS AND ATOMIC STRUCTURE

First ideas about Atom (for 200 years)
R.Boyle (1661)
I.Newton (1687, 1704)
Proposing Atom Theory : J.Dalton (1803-1807)
Dalton atom theory
chemistry laws.

depends

on

known

experiments

and

ELECTRONS
M.Faraday: ran an important series of experiments on chemical
electrolysis.
In the experiments, compounds are decomposed by electricity.
He studied the relationship between the amount of electricity
used and the amount of compound decomposed.
(1834)
J.J.Stoney (1874): proposed that units of electrical charge are
associated with atoms.
Then, he suggested that these units be called
(1891).

electrons

Further information on electrons at the end of 19th century

using Cathode-Ray tubes.
Attempts to pass an electric current through a vacuum led to
the discovery of cathode rays.
Two electrodes are sealed in a glass tube from which air is
completely removed.

When a high voltage is impressed across these electrodes, rays

stream from the negative electrode (cathode).
These rays are negatively charged, travel in straight lines, and
cause the walls opposite the cathode to glow.

Properties of cathode rays:

Travel in straight lines

They are invisible

Have properties that are independent of the material from

which they originate.

They are deflected by electric and magnetic fields in the

manner expected for negatively charged particles.

Charge-to-Mass Ratio of Electrons (e/m)

J.J. Thomson (1897): measured deflection of cathode rays by
electric and magnetic fields.
The values of e and m cannot be measured separately, by
Thomson method.
e/m =

-1.76x1011 C/kg

Charge of Electrons
R.A. Millikan (1908)
Charge of an electron, -1.6x10-19 C
Using the value of e/m =

-1.76x1011 C/kg

Mass of an electron, 9.1x10-31 kg

POSITIVE IONS (CANAL RAYS)

Particles carrying positive charge were also discovered in cathode

ray tubes.
Positive Rays
Goldstein (1886)
Charge of a proton: 1.6x10-19 C
Mass of a proton: 1.67x10-27 kg (1836 times of mass of electron)

THE NUCLEAR ATOM

E. Rutherford (1911)

Most of the mass and all of the positive charge of an atom are
centered in a very small region called the nucleus. The atom
is mostly empty space.

The magnitude of the positive charge is different for different

atoms and is approximately one-half the atomic weight of the
element.

There exist as many electrons outside the nucleus as there

are units of positive charge on the nucleus. The atom as a
whole is electrically neutral.

Since atomsa re electrically neutral, a give atom must contain as

many electrons as protons.

Rutherford (1920)

Chadwick (1932)

the existence of an uncharged particle.

the existence of neutron

Mass of a neutron: 1.6749x10-27 kg

Properties of Three Fundamental Particles

Particle

Proton
Neutron
Electron

Mass
kg

1.67x10-27
1.67x10-27
9.11x10-31

1.007277
1.008665
0.000549

Charge
C
Atomic
Electric
charge
-19
+1.6x10
+1
0
0
-19
-1.6x10
-1

MASS SPECTROMETER, ISOTOPS, ISOBARS

The atomic mass unit (amu) : is defined as exactly 1/12 of the
mass of the atom known as carbon-12 (carbon twelve).

12
6

The unit is u.
Atomic number (Proton number): The number of protons in the
nucleus of an atom (Z).
The number of electrons in an electrically neutral atom is also
equal to the atomic number Z.
The mass of an atom is determined by the total number of protons
and neutrons in its nucleus.
This total is called the mass number, A.
The number of neutrons in an atom, the neutron number, is A - Z.
Element Atom:
A
Z

X
X: Symbol of Element

Z: Atomic number
A: mass number
(total number of protons and neutrons in its nucleus)

neutron number = A Z

All atoms of a given element have the same atomic number.

Some elements, however, consist of several types of atoms that
differ from one another in mass number.
Isotopes: atoms that have the same atomic number but different
mass numbers (F.Soddy).
The mass spectrometer is used to determine the types of isotopes
present in an element, the exact atomic masses of these isotopes,
and the relative amount of each isotope present.

Isotopes: elements having the same atomic number, but

different atomic mass. Chemical properties same.
Example: Cl: 2 natural isotopes.

35
17

Cl

37
17

Cl

In each atom, there are 17 protons, 17 electrons.

18 neutron

20 neutron

Isobars: elements having different atomic number, but same

atomic mass. Chemical properties different.
36
16

36
18

Ar

Nucleon
different.

number

same,

proton

and

neutron

numbers

S isobar: 16 protons, 20 neutrons

Ar isobar: 18 protons, 18 neutrons
Chemical properties depend on the number of electrons.

Isotons: number of neutrons same, number of protons

different.
35
17

Cl

36
18

Ar

number of neutrons same: 18

number of protons different

The mass spectrometer is used to determine the types of isotopes

present in an element, the exact atomic masses of these isotopes,
and the relative amount of each isotope present.

Example: 3 Neon isotopes

20
10

Ne

21
10

Ne

22
10

Ne

Neon isotopes and the relative amount of each isotope:

20
10

Ne

19.992 u
%90.92

21
10

Ne

22
10

Ne

20.994 u
%0.26

21.99 u
%8.82

Atomic mass of Neon Atom: 20.18 u (Average atomic mass of

Neon)

ELEKTROMAGNETIC RADIATION
Further detailed information on the structure of Atom were
obtained by studies on emission and absorption of electromagnetic
radiation by atoms.

Elektromagnetic
characteristics.

radiation

carries

both

wave

and

particle

Types of electromagnetic radiation:

Radio waves
Infrared waves
Visible light
X-rays

Electromagnetic Radiation travels through space in a wave motion.

The following terms are used to describe these waves:

The wavelength (): is the distance between two similar

points on two successive waves.

Number of waves ( ) : 1/

Amplitude (a) :
depth )

The intensity (or brightness) of the radiation is proportional

to the square of the amplitude, a2.

In vacuuum, all waves, regardless of wavelength, travel at

the same speed, 3x108 m s-1. This speed is called the speed
of light and is given the symbol c.

Frequency of radiation (): the number of waves that pass a

given spot in a second.

of a wave is the height of a crest (or the

= c/
c=
Example: Find the frequency of radiation which has a wavelength
of 1.54x10-10 m.
frequency (): Hertz (Hz)
1 Hz = 1 devir/s = 1/s = s-1
= c/

C = 3.00x108 m s-1
= 1.54x10-10 m
= 3.00x108 mHz /(1.54x10-10 m) = 1.95x1018 Hz
Wavelengths of Different Elektromagnetic Radiation Types:
White (visible light) 4x10-5 cm - 8x10-5 cm
4000 A-8000 A
400-700 nm

ATOMIC SPECTRA

During chemical reactions, electrons surrounding the nucleus

react, not the atoms.

The properties of elements depend on the configuration of

electrons.

The best method to find the configuration of electrons for

elements is by the investigation of atomic spectra.

When gases or vapors of a chemical substance are heated in

an electric arc or a Bunsen flame, light is emitted.

If a ray of this light is passed through a prism, a line

spectrum is produced.

This spectrum consists of a limited number of colored lines,

each of which corresponds to a different wavelength of light.

The line spectrum of each element is unique.

Hydrogen Spectrum:
The frequencies that correspond to the lines in the visible region
of the hydrogen spectrum are given by the equation:
Balmer (1885) series:

1
1
1
10967758 m 1 ( 2 2 )

2
n

3.29 x 10 15 Hz (

1
1
2 )
2
2
n

=wavelength of radiation
= frequency of radiation.
n = 3,4,5
Example: for n= 3, wavelength of line in the spectrum.

1
1 1
10967758 m 1 ( 2 )

9
2

= 1523300 m-1

= 6.564x10-7 m = 656.4 nm
n= 4
n= 5

= 486.3 nm
= 424.3 nm

n= 6

= 410.3 nm

Wavelengths of hydrogen emission spectra in the visible region.

Rydberg Equation
For Hydrogen

1
1
1
10967758 m 1 ( 2 2 )

n1
n2
10967758 m 1 : Rydberg constant

n1, n2 : 1,2,3,
n2 n1
n1 = 1,
n1 = 3,

n2 = 2,3,4, Spectrum lines in Lyman series.

Spectrum lines in Paschen series.

n1 = 4, Spectrum lines in Brackett series.

n1 = 5 ,

Spectrum lines in Pfund series.

Example: Find the wavelength of 3rd spectrum line in Brackett

series for Hydrogen spectrum.
1
1
1
10967758 m 1 ( 2 2 )

4
7

= 2.166x10-6 m = 2166 nm

BOHR ATOMIC THEORY

N.Bohr (1913): proposed a theory for electronic structure of atoms
depending on,

Rutherfords model
Plancks kuantum theory (developed by Einstein)
Hydrogen Atomic spectrum
The hydrogen atom contains one electron and nucleus that
consists of a single proton.
Bohrs theory includes the following:

The electron of the hydrogen atom can exist only in spherical

orbits (which are also called energy levels or shells).
These shells are arranged concentrically around the nucleus.
Each shell is designated by a letter (K, L, M, N, O,) or a
value of n (1, 2, 3, 4, 5, ).

The electron has a definite energy characteristic of the orbit

in which it is moving. The K level (n=1), the shell closest to
the nucleus, has the smallest radius.
An electron in the K level has the lowest possible energy.
With increasing distance from the nucleus (K, L, M, N, O,; n
=1, 2, 3, 4, 5, ), the radius of the shell and the energy of an
electron in the shell increase.
The electron cannot have an energy that would place it
between the permissible shells.

When the electrons of an atom are close to the nucleus as

possible (for hydrogen, one electron in the K shell), they are
in the condition of lowest possible energy, called the ground
state.
When the atoms are heated in an electric arc or Bunsen
flame, electrons absorb energy and jump to outer levels,
which are higher energy states. The atoms are said to be in
excited states.

When an electron falls back to a lower level, it emits a

definite amount of energy.

The energy difference between the high energy state and low
energy state is emitted in the form of a quantum of light.
The light quantum has a characteristic frequency (and wavelength) and produces a characteristic spectral lines.
In spectral studies, many atoms are absorbing energy at the
same time that many others are emitting it.
Each spectral line correspond to a different electron transition.
Bohr derived an equation for the energy that an electron would
have in each orbit,
Energy of elektron,
1
n2

E A

(Bohr)

A= 2.18x10-18 J
n= 1,2,3,,

(Principal Kuantum Number)

E = - value
Energy of the photon emitted,
E E n 2 E n1

( A

A(

1
n2

1
n1

) ( A

1
n2

For energy of photon,

1
n1

h h

A(

1
n1

n2

A
1
1
( 2
)
2
h c n1
n2

A/hc = 10973731 m-1

10973731 m 1 (

1
n1

1
n2

n= 1 K shell
n= 2 L shell
n= 3 M shell

PROBLEMS:
1. What is the atomic weight of magnesium? The element
consists of
78.70 %

24
12

Mg

atoms (mass, 23.99 u),

10.13 %

25
12

Mg

atoms (mass, 24.99 u), and

11.17 %

26
12

Mg

atoms (mass, 25.98 u).

12

13

2. Carbon occurs in nature as a mixture of 6 C and 6 C

12
The atomic mass of
6 C is exactly 12 u, by definition, and the
13
atomic mass of 6 C
is 13.003 u. The atomic weight of carbon
12
is 12.011 u. What is the atom percent of 6 C in natural carbon?

3. What are the frequency and wavelength of line in hydrogen

spectrum that corresponds to an electronic transition from the
n= 3 level to n = 2 level?

ATOMIC NUMBERS AND THE PERIODIC LAW

Relations between Elements (early in the 19th century)
Dbereiner (1817,1829) : properties of sets of elements that he
called triads:
Ca, Sr, Ba
Li, Na, K
Cl, Br, I
S, Se, Te
The elements of each set have similar properties
Newlands (1863-66): when the elements are listed by increasing
atomic weight, the eighth element is similar to the first, the ninth
to the second, and so forth.
Meyer, Mendeleev (1869): modern periodic classification of the
elements in order of increasing atomic weight.

Modern Periodic Law: physical and chemical

elements are function of atomic numbers.

properties

of

When the elements are listed according to their atomic numbers,

similar properties are observed periodically.
Mendeleevs table listed the elements in such a way that similar
elements appeared in vertical columns, called groups.
Atomic numbers and atomic masses increase in paralel (except K,
Ni ve I) .
Moseley studied the X-ray spectra of 38 elements with atomic
numbers between 13 (aluminum) and 79 (gold).
Using a corresponding spectral line for each element, he found
that there is a linear relationship between the square root of the
frequency of the line and the atomic number of the element.
(Elementlerin X-nlar spektrumunun uygun bir izgisinin
frekansnn karekk ile elementin atom numaras arasnda
izgisel bir bant olduu)
a Z b

a= 5.0x107
b= 1.0
The the square root of the frequency of the spectral line
increases by a constant amount from element to element when the
elements are arranged by increasing atomic number.
Atomic number is equal to the positive charge in nucleus.
Atomlar farklandran zellik ekirdekteki art yk says, yani
proton says (ntral atomlar iin buna eit olan elektron says)
ATOM NUMARASI

3. PERIODIC TABLE
In the Modern periodic table, elements are arranged according
to increasing atomic numbers.
When the elements are listed according to their
numbers, similar properties are observed periodically.

atomic

Elements having similar physical and chemical properties

listed vertically.
Vertical columns
similar properties

(Groups) :

are

bring together elements with

Horizontal rows (Periods) : elements are arranged in order of

increasing atomic numbers.
There are 7 periods in the Periodical Table:
1st Period: 2 elements (H, He)
2nd Period: contains 8 elements

3rd Period: contains 8 elements

4th Period: contains 18 elements
5th Period: contains 18 elements
6th Period: 32 elements
Lanthanides : 14 elements placed at the bottom of the table
7th Period:
Actinides: 14 elements placed at the bottom of the table
Group I- Group VII
Group VIII (Inert gases)
A group: main- group elements
B group: transition elements IB VIII B
Group VIII B : contains totaly 9 elements: 3 rows and 3 element
in each row.
Each period starts with an alkali metal (I A Group) and ends
with an inert gas (VIIIA Group).
Before the inert gas, there is a
Group).

halogen (ametal)

(VII A

In each period, property of elements changes from strong metal

to ametal.
After strong metal property, then inert gas.
In the periodic table, elements are listed according to the
electronic configuration of elements.
Elements are
properties.

also

arranged

according

to

their

chemical

The maximum number of electrons each energy level (shell)

contain: 2n2
n: pricipal quantum number of each energy level

n: 1

K shell

2 electrons

n: 2

L shell

8 electrons

n: 3

M shell

18 electrons

n: 4

N shell

32 electrons

n: 5

O shell

50 electrons

QUANTUM NUMBERS
1.

Pricipal quantum number, n

:1

Letters designating shells

:K

Energy levels in an atom

Pricipal quantum number, n identifies the shell, or level,
to which the electron belongs.
The larger the value of n, the farther the shell is from the
nucleus.
2. Subsidiary quantum number, l
Each shell consists
sublevels.

of one

or

more subshells,

or

The number of subshells in a principall shell is equal to

the value of n.
There is only one subshell in the n=1 shell, there are
two in the n=2 shell.
The values of l for the sublevels of a shell are
determined by the shells value of n.
There is one value of l for each term in the series.
l = 1, 0, 1, 2 , 3, n-1
n=1, l=0

K shell consists of 1 subshell.

n=2, l=0, 1

L shell consists of 2 subshells.

The number of subshells in a principal shell

quantum number of shell

= principal

Subsidiary quantum number, l

:0

Notation

:s

In the ground state of an atom, electrons fill

subshells.

5
h

6..
i..

s, p, d and f

To designate the subshell in a principal shell, quantum number

n and subsidiary quantum number l are written together.
For example, second shell (n=2) (L shell), s ve p subshells, we
designate as:
2s (n=2, l=0) and

2p (n=2, l=1)

3. Magnetic orbital quantum number, m:

Each orbital within a given subshell is identified by a magnetic
orbital quantum number, m.
For any subshell, the values of m are given by the terms in the
series,
m= -1,.., + 1 all values
Example: l=0, m=0
s subshell contains 1 orbital (s orbital)
p subshell contains 3 orbitals: l=1, m= -1, 0, +1 (3 orbitals, 3
p orbitals)
d subshell contains 5 orbitals
f subshell contains 7 orbitals.
i.

As the value of n increases, energy of the shells increases.

ii.

As the value of n increases, energy difference between the

shells decreases.
Consequently, energy level of 4s is lower than 3d.
5s is lower than 4d.
6s and 4f are lower than 5d.

iii.

Orbitals of subshells are designated with a short line.

4. Magnetic Spin Quantum Number (s) . Pauli Principle

An electron in an orbital has properties that can be explained
by assuming that it spins on its own axis.
Since only two directions of spin are possible, there are only two
values of m.
s= +

s= -

A spinning charge generates a magnetic field. Each electron,

therefore, has a magnetic moment associated with it because of
its spin.
Magnetic moments of two electrons that spin in opposite
directions cancel each other. Each orbital can hold two electrons
with opposite spins.

Consequently:
Each electron may be described by a set of 4 quantum numbers:
n, l, m and s.
1. n gives the shell and the relative average distance of the
electron from the nucleus.

2. l gives the subshell and the shape of the orbital fort he

electron. Each orbital of a given subshell is equivalent in
energy.
3. m designates the orientation of the orbital.
4. s refers to the spin of the electron.

Pauli Exclusion Principle: states that no two electrons in the same

atom may have identical sets of all 4 quantum numbers.
Even if two electrons have the same values for n, l, m, they will
differ in their s values.
This situation indicates that two electrons are paired in a single
orbital.
Two electrons paired in a 1s orbital, for example, have (n, l, m, s)
quantum sets of (1, 0, 0, +) and (1, 0, 0, -).
According to the exclusion principle, therefore, an orbital may hold
no more than two electrons.
(rnein, bir yrngeye ait n, l ve m deerleri belliyse, s deerleri
farkl olmak zorunda.
Yrngede farkl s deerli 2 elektron bulunabilir:
s= +

s= -

O halde bir yrngede 2 elektron vardr ve bu elektronlarn

spinleri zttr.
Pauli ilkesi bir yrngedeki elektron saysn 2 ile snrlar.)

Quantum numbers, shells, subshells, orbitals

Principal
quantum

Shell

Subsidiary
quantum

Subshell

Magnetic
quantum

Orbital
number

number,
n

number, l

1
2

K
L

number, m

0
0
1
0
1
2

1s
2s
2p
3s
3p
3d

0
0
-1,0,+1

0
1
2
3

4s
4p
4d
4f

0
-1,0,+1
-2,-1,0,+1, +2
-3,-2,-1,0,+1,
+3

0
-1,0,+1
-2,-1,0,+1, +2

Maximum number of electrons in Subshells

Subshell
Number
of Maximum
number
orbitals
electrons
s
1
2
p
3
6
d
5
10
f
7
14
Maximum number of electrons in Shells
Shell
n
Subshell
K
L
M
N

1
2
3
4

1s
2s, 2p
3s, 3p, 3d
4s, 4p, 4d, 4f

in
subshell
1
1
3
1
3
5
1
3
5
+2,
7

of

Maximum
number of
electrons
2
8
18
32

Maximum number of electrons that a shell can hold: 2n 2

According to quantum numbers and Pauli exclusion principle, each
orbital can hold two electrons.
Magnetic properties of atoms:
Electron spin magnetic properties of atoms and molecules

The number of unpaired electrons in an atom, ion, or molecule can

be determined by magnetic measurements.
There are 3 types of magnetic properties:
Diamagnetism
Paramagnetism
Ferromagnetism
Diamagnetic substances: are weakly repelled by a magnetic field.
A material is diamagnetic if all its electrons are paired.
Paramagnetic substances:
electrons are paramagnetic.

substances that contain unpaired

The magnetic moment depends upon the number of unpaired

electrons present.
Two effects contribute to the paramagnetism of an atom:

The spin of the unpaired electrons.

The orbital motion of these electrons.

Ferromagnetic substances: the most important is iron

Ferromagnetism is much stronger than paramagnetism.
ELECTRONIC CONFIGURATION OF ELEMENTS
The electron configuration of an atom is a designation of the
distribution of its electrons among the different electronic shells
and orbitals.
Electronic configuration of elements according to the increasing
energy levels
Electrons occupy the orbitals in such a way as to minimize the
energy of the atom.
Order in which electrons occupy orbitals,
first the 1s
then 2s
2p

The order of filling of electronic subshells:

1s
2s
3s
4s
5s
6s
7s

2p
3p
4p
5p
6p
7p

3d
4d 4f
5d 5f
6d

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f,
6d, 7p,
No two electrons in an atom may have all four quantum numbers
alike- the Pauli exclusion principle.

The electron configuration of an atom is represented in two

different ways:
1. spdf notation
(alt tabaka
yazarak)

simgeleri

zerine

ierdikleri

elektron

saysn

2. orbital diagram
(daha ayrntl bir biimde, yrngeleri ksa izgi ile spinleri
farkl 2 elektronu bunun zerinde aa ve yukar ynl 2 okla
gstererek-yrnge diyagram)

Examples:
1

H : 1s1

He : 1s2

Li : 1s2 2s1

Be : 1s2 2s2

: He 2s1
: He 2s2

Elementlerde elektron dizilii sras

Fig 4.5.1: Book Important NEML

(ENDER ERDK, YKSEL SARIKAYA,

KMYASI, GAZ KTABEV, 19.BASKI)

TEMEL NVERSTE

HUNDS RULE: states that the electrons are distributed among the
orbitals of a subshell in a way that gives the maximum number of
unpaired electrons with paralel spins.
The term paralel spin means that all the unpaired electrons spin in
the same direction.
All the magnetic spin quantum number (s) values of these
electrons have the same sign. (Rule of Maximum Multiplicity)

PARTS OF PERIODIC TABLE AND TYPES OF ELEMENTS

Figure 4.6.1: s,p, d and f blocks in the periodic table
IA, IIA Group elements: s subshells full
s block (2 elements in each row )
IIIA- VIIIA Group elements: p subshells full
p block (6 elements in each row )
IB- VIIIB Group elements: d subshells full
d block (basic transition elements) (10 elements in each row)
4f ve 5f subshells full, inner transition elements
(lantanides and actinides): f block

Elements can have similar properties according to being s, p, d and

f blocks, and can be classified into 4.
Elements can also be classified accoding to being A and B groups.

Classification of elements into metals and nonmetals is based on

certain properties.
Metals are good conductors of heat and electricity,
characteristic of luster, are malleable, anda re ductile.

hace

Nonmetals are very poor conductors of heat and electricity, are

not lustrous anda re brittle in the solid state.
The elements may also be classified according to their electron
configuration:
1. Noble gases: In the table, they are found at the end of each
period in goup 0.
They are colorless monatomic gases, which are chemically
unreactive, and diamagnetic.
ns2np6
2. The representative elements: found in the A families of the
periodic table.
include metals and nonmetals
some are diamagnetic, some are paramagnetic
all of their electronic shells are either complete or stable
(ns2np6)
3. The transition elements: are found in the B families of the
periodic table (d electrons)
most of them paramagnetic, form highly colored
paramagnetic compounds.
4. The inner transition elements: found at the bottom of the
table.
6th periods: lanthanides series
7th periods: actinide series

(f electrons)
paramagnetic compounds

4. CHEMICAL BONDING
Chemical bonds, which form when atoms combine, are the
result of changes in electron distribution.
There are 3 types of bonding:
1. Ionic bonding: result when electrons are transferred from
one type of atom to another.
The atoms of one of the reacting elements lose electrons and
become +vely charged ions.
The atoms of the other reactant gain electrons and become
-vely charged ions.
The electrostatic attraction between the oppositely charged
ions holds them in a crystal.

2. Covalent bonding: electrons are shared, not transfered.

A single covalent bond consists of a pair of electrons shared
by two atoms.
Molecules are made up of atoms covalently bonded to each
other.
3. Metallic bonding: found in metals and alloys.
The metal atomsa re arranged in a three-dimensional
structure.
The outer electrons are free to move anda re responsible for
binding it together.

ATOMIC PROPERTIES
The properties of elements in the periodic table change:
from left to right in a period,
from top to bottom in a group.
Most of these properties can be explained according o the
electron configuration of the elements:
1.
2.
3.
4.

atomic size
ionization energy
electron affinity
electronegativity

Atomic size:

The size of an atom can be taught as the distance from the

nucleus to the outer-shell electron(s). Let us call this distance
the atomic radius.
For isolated atoms the atomic radius is known as the van der
Waals radius.
For bonded atoms we speak of a covalent radius, ionic radius
and in the case of metals, a metallic radius.
The covalent radius is one- half the distance between the nuclei
of two identical atoms covalently bonded together.
Variation of Atomic Sizes within a Group of the Periodic Table:
The more electronic shells in an atom (the farther down a grou
of the periodic table) the larger the atom.
Variation of Atomic Sizes within a Period of the Periodic Table:
The atomic size decreases from left to right through a period of
elements.
(Bir grupta, yukardan aaya inildike atom yarap artar,
nk etkin ekirdek yk sabit kalmakla beraber yukardan
aaya doru n says ve elektron tabakalarnn says artar ve
atom byr.)
(Bir periyotta soldan saa atom yarap azalr, ayn periyotta n
says deimemekle beraber atom numaras yani etkin ekirdek
yk arttndan en d tabaka elektronlar daha ok ekilir ve
atom klr.)
(Temel gei elementlerinde ve i gei elementlerinde atom
yarapndaki deime dier elementlere gre daha az, nk
elektronlar daha iteki alt tabakalara yerleir.)
Cations (positive ions) are smaller than the atoms from which
they are formed.
Anions (negative ions) are larger than the atoms from which
they are formed.

Ionization Energy:
The ionization energy (I) of an atom is the amount of energy
that the gaseous atom must absorb so that its most loosely held
electron may be stripped from the atom.
(Gaz halinde ntral bir atomdan bir elektron uzaklatrmak iin
verilmesi gerekli enerji)
(yonlama enerjisi, bir atomun elektronlarndan birini koparp
sonsuz uzakla gtrmek ve bir fazla art ykl yeni bir atom
oluturmak iin gerekli enerji)
X (g) + Energy X+ + e

Energy= ionization energy

endothermic process
Ionization energies decrease as the sizes of atoms increase.
Electron Affinity:
EA is the amount of energy
electron by a gaseous atom.

associated with the gain of an

(ntral bir atomun bir elektron yakalamas srasnda aa kan

enerji)
X (g) + e- X- + Energy

Energy= Electron Affinity

Exothermick process
Electron Affinities become smaller (more negative) from left to
right across a period of the periodic table and become larger
(less negative) from top to bottom within a group.
Electronegativity:
(Mulliken): ionization energy + electron affinity (1934).
Pauling: is a measure of tendency of atoms attracting electrons
in a molecule

(bir atomun bir moleklde elektronlar ekme eiliminin bir

ls)
Mulliken: measure of tendency of atoms attracting electrons in
a molecule can be found by arithmetic average of ionization
energy + electron affinity.
(Elektronegatiflik: bir atomun bir kimyasal bada elektron
iftini ekme eiliminin bal ls)
(Figure 4.8.5 Periyotlu dizgede atom
enerjisi ve elektronegatifliin deimesi)

yarap,

iyonlama

Lewis symbols: of elements consist of the common chemical

symbol surrounded by a number of dots.
The dots represent the outer shell or valence electrons.
Si: 1s2 2s2
2p6
3s2
3p2

..
Si .
.
The relation between position in the periodic classification and
atomic properties
In a period, from left to right:

Atomic size decreases

Ionization energy increases
Electron affinity decreases
Electronegativity increases
Metallic character decreases
Nonmetallic character increases
In a group, from top to bottom:

Atomic size increases

Ionization energy decreases
Electron affinity increases
Electronegativity decreases
Metallic character increases
Nonmetallic character decreases
QUESTIONS
1.

5. CHEMICAL CALCULATIONS
1 mole : atoms or molecules in 0.012 kg
0.012 kg

12
6

12
6

C (carbon-12).

C contains 6.022x1023 atoms (Avogadro number)

1 mole element contains Avogadro number atoms,

1 mole compound
Avogadro number molecules.
Examples,
1 mol O, contains 6.022x1023 O atoms
1 mol O2 , contains 6.022x1023 O2 molecules.
1 mol Ca , contains 6.022x1023 Ca atoms
1 mol Ca2+ , contains 6.022x1023 Ca2+ ions
1 mol CaCl2 , contains 1 mol Ca2+ ions, 6.022x1023 Ca2+ ions,

2 mol Cl2- ion, 2x6.022x1023 Cl2- ions.

1 amu (atomic mass units) (1 u) : mass of 1/12 of 1

Mass of 1

12
6

12
6

C atom.

C atom = 12,0000 u.

1 atom O, 16 u
1 mol O, 16 g
Mass of 1 mol atom, atomic mass in grams.
1 mol karbon-12, 12,0000 g
1 mol O2 (1 molecule-gram O2), 32 g
Mass of 1 mol molecule, molecule mass in gram.
Molecular weight of CCl4: 12 u + 4x35.5 u = 154 u
Molecular weight: g mol-1
Example:
C + 2 Cl2 CCl4
1 mol C reacts with 4 mol Cl or 2 mol Cl2 and 1 mol CCl4 is
formed.

QUESTIONS

2.65 mol CaCl2: how many moles Ca and Cl?

30.5 g Si: how many moles Si?

5.1 mol Cu: find g of Cu

How many moles of Ca with 2.5 moles of O2 should be used in

order to prepare CaO?

What amount of Ca (grams) should be used with 41.5 g Cl2 in

order to prepare CaCl2 ?

What is the mass of 1 Ca atom in g?

How many atoms are there in 2.0 g Na?

What is the % composition of CHCl3 (chloroform) ?

How many grams is 1 u?

Find the amount of Fe in 10 g Fe2O3.

Nicotine sample contains C, H and N. A 0.6075 g sample is

reacted with oxygen and 1.65 g CO2, 0.4725 g H2O was
obtained and 0.105 g N2 was left. What is the composition of
nicotine?

FINDING CHEMICAL FORMULAS

Chemical Formula of a compound provides the following
information:
i. Element composition
ii. Relative number of elements formed
iii. Real number of elements formed
iv. Structure
Simple Formula (emprical formula) : i, ii
Molecule formula: i, ii, iii
Structure formula:
i, ii, iii, iv

Simple Formula:
NaCl, KCl, H20, CH2
Molecule formula:
H20: water
C2H4: ethylene

simple formula: CH2

C3H6: propylene

simple formula: CH2

Structure formula

H2C=CH2 : ethylene
H3C-C-OH : asetic asid

O
Molecule formula: C2H4O2
simple formula: CH2O

QUESTIONS:
1.
A gas sample contains 2.34 g N and 5.34 g O.
What is the simple formula of this sample? If the molecular weight
is 92 u, what is the molecular formula?
2.
A fosforous oxide contains 43.7 % P ve 56.3 %
O. What is the simple formula of this sample? If the molecular
weight is 284 u, what is the molecular formula?
3.
A cafein sample contains 0.624 g C, 0.065 g H,
0.0364 g N and 0.208 g O after combustion. Molecular weight is
194 g mol-1dir. What is the simple formula and the molecular
formula of this sample?
4.
Ethyl alcohol contains C, H and O. 0.1 gram of
ethyl alcohol is reacted with oxygen and 0.1910 g CO2 and 0.1172
g H2O was obtained. What is the simple formula of ethyl alcohol?
5.
A 2.1 g of salt sample containing crystal water
was heated and 0.57885 g H2O and 1.52115 g dehydrated salt was
obtained. It was found that the dehydrated salt contains 0.2991
g Fe2+, 0.1932 g NH4+, 1.02885 g SO42-. What is the simple formula
of this sample?
6.
A 0.1685 g sample of an organic compound was
combusted and S was obtained as SO42- ion and then reacted with
Ba(OH)2 solution and 0.22185 g BaSO4 was obtained. Cl in a
0.19515 g sample was obtained as Cl- ion and reacted with AgNO3
to obtain 0.1180 g AgCl. Find the % composition of S and Cl of
the sample.

REACTIONS. REACTION EQUATIONS

1. reactions in which electron transfer takes place between the

reactants and products (oxidation-reduction reactions- redox
reactions.
2. reactions in which electron transfer does not take place
between the reactants and products.
Reactions can be written as,
1. molecule reaction
2. ion reaction
3. net ion reaction
4.
Example:
Molecule reaction
NaCl (aq) + AgNO3 (aq) AgCl (s) + NaNO3 (aq)
Ion reaction
Na+ (aq) + Cl- (aq) + Ag+ (aq) + NO3- (aq)
AgCl (s) + Na+ (aq) + NO3- (aq)
Net ion reaction
Ag+ (aq) + Cl- (aq) AgCl (s)

QUESTIONS
1. Hot iron reacts with water vapor and H2 and Fe3O4 are
formed. Write the reaction and balance the reaction.
2. Balance the combustion of octane, C8H18.

OXIDATION AND REDUCTION

There are two methods for balancing the oxidation-reduction
reactions:

Changing oxidation number method

Ion-electron method
oxidation-reduction: electron transfer
oxidation: increase of oxidation number of an atom (loosing
electron)
reduction: decrease of oxidation number of an atom (gaining
electron)
Reductant (ndirgen): atom whose oxidation number increased
(atom loosing electron) (oxidized).
Oxidant (Ykseltgen): atom whose oxidation number decreased
(atom gaining electron) (reducted).
Oxidation number: electron charge of an atom (bir atomun sahip
olmu grnd elektron yk)
Finding oxidation numbers :
1. Oxidation number of an atom in an element is zero
Ne, H2, F2, P4, S8
2. For simple ions, oxidation numbers:
Na+, Al3+, S2- ions oxidation numbers +1, +3 ve -2.
3. In a neutral compound, the sum of the oxidation numbers is
0.
In a complex ion, the sum of the oxidation numbers of atoms
(Bir kompleks iyonun (ok atomlu iyon, polatomik iyon)
yk, atomlarn ykseltgenme saylar toplamna eittir.)
4. oxidation number of
5. oxidation number of
lithium hydride LiH)
6. oxidation number of

F in all of its compounds is -1.

H in its metal hydrides is (for example
-1, in all the other compounds +1.
O is -2.

OF2 +2
Peroxides -1 (hydrogen peroxide, H2O2)

Speroxides -1/2 (potassium superoxide, KO2)

7. IA Group elements (except H) oxidation number is +1,
IIA Group elements oxidation number is +2.
8. VIIIA Group elements (halogens) metal hydrides oxidation
number is -1.
E.g. : NaI, FeBr2, CrCl3
oxidation number changes in other compounds of Halogenes.
E.g. : KClO, KClO2, ClO2, KClO3, KClO4 Compounds,
oxidation number of Cl is, respectively:
+1, +3, +4, +5, +7dir.
9. oxidation number may be an integer or not.
QUESTION
1. Find the oxidation numbers of the atoms in the following
compounds or ions:
KNO3, Ca3 (PO4)2 , Cr2O72-

BALANCING CHEMICAL EQUATIONS

In an oxidation-reduction reaction, number of electrons lost
should be equal to the electrons gained
(bir ykseltgenme-indirgenme reaksiyonunda, ykseltgenme
ileminde verilen elektron saysnn, indirgenme ileminde alnan
elektron saysna eit olmas gerekmektedir.)

Steps:
1. Write the oxidation numbers of each atom in the equation
(Her atomun ykseltgenme says, denklemde altna yazlarak
belirtilir.)
2. Find the atoms that the oxidation numbers changed and
determine the number of electrons changed.
(Ykseltgenme says deien atomlar bulunur, atom bana
alnan ve verilen elektron says belirlenir.)
3. If the element atoms are more than one, then number
electrons per compound are determined.
(bileikte element atomu says birden fazlaysa, bileik
forml bana alnan ve verilen elektron says bulunur. )
4. Balance the electrons transfered
(Alnan ve verilen elektron says, ykseltgen ve indirgen
atom
ve/veya bileiklere uygun katsaylar yazarak
eitlenir.)
5. According to conservation mass, balance the remaining
atoms
(Ktlenin korunumu yasasna gre dier katsaylar konulur.)
These steps can also be applied to the ion reactions
(Ykseltgenme says deimesi yntemi, iyon denklemlerine de
uygulanr.)

QUESTIONS
1. Balance :
Cu + HNO3 Cu(NO3)2 + NO + H2O
Cu + HNO3 Cu(NO3)2 + NO + H2O
0 +1+5-2
+2+5-2
+2-2 +1-2
Cu0 -2 e- Cu2+

N5+ +3 e- N2+
3/Cu0 -2 e- Cu2+
2/ N5+ +3 e- N2+
3 Cu0 -6 e- 3 Cu2+
2 N5++6 e- 2 N2+
3Cu + HNO3 3Cu(NO3)2 + 2 NO + H2O
2. Balance :
KMnO4 + H2SO4 +FeSO4 K2SO4 + MnSO4 + Fe2(SO4)3 + H2O
KMnO4 + H2SO4 +FeSO4 K2SO4 + MnSO4 + Fe2(SO4)3 + H2O
+1+7-2 +1+6-2 +2+6-2 +1+6-2 +2+6-2 +3 +6-2 +1-2
Mn+7 +5 e- Mn2+
Fe2+ - e- Fe3+
Mn+7 +5 e- Mn2+
2Fe2+ -2 e- 2Fe3+
2/ Mn+7 +5 e- Mn2+
5/ 2Fe2+ -2 e- 2Fe3+
2 Mn+7 + 10 e- 2Mn2+
10 2Fe2+ -10 e- 10 Fe3+
2KMnO4 + 8H2SO4 +10FeSO4
K2SO4 +2MnSO4 + 5Fe2(SO4)3 + 8H2O

3. Balance :
Cr2O72- + Cl- Cr3+ + Cl2

Cr2O72- + Cl- Cr3+ + Cl2

+6
-1
+3
0
Cr6+ +3e- Cr3+
Cl- - e- Cl0

2Cr6+ +6e- 2Cr3+

2Cl- -2e- Cl20
2Cr6+ +6e- 2Cr3+
3/2Cl- -2e- Cl20
2Cr6+ +6e- 2Cr3+
6Cl- -6e- 3 Cl20
Cr2O72- + 6Cl- 2Cr3+ + 3Cl2
Cr2O72- + 6Cl- +14H+ 2Cr3+ + 3Cl2 +7H2O

CALCULATIONS DEPENDING ON CHEMICAL REACTIONS

Combustion of Ethylene
H2C=CH2 + 3O2 2CO2 + 2H2O
1 molecule ethylene reacts with 3 molecules oxygene and, 2
molecules carbon diokside and 2 molecules water is formed.
1 mol ethylene reacts with 3 mol oxygene and, 2 mol carbon
diokside and 2 mol water is formed.
For 5 mol ethylene, for the completion of the reaction 15 mol
oxygene is required.
If 5 mol ethylene and 12 mol oxygene are present, for the
reaction of 5 mol ethylene, we need 15 mol oxygene. So, 12 mol
oxygene will react with only 4 mol ethylene, and 1 mol ethylene
will be left.
Oxygen (limiting element)
Number of moles of the products will be determined by the
limiting element.

(Snrlayc madde: reaksiyonda ilk nce kaybolan ve reaksiyonun

yrmesini engelleyen madde)

% yield: relates the amount of product that is actually obtained

(actual yield) to the amount that theory would predict (the
theoretical yield).
% yield = (actual yield/ theoretical yield) x 100 %

If 1 mol ethylene reacts with 3 mol oxygene, then theoretically

we expect to form 2 mol carbon dioxide and 2 mol water.
In the above example, if 1.5 mol mol carbon diokside is formed,
% yield= (1.5/2)x100 = 75 %

1.GASES
PROPERTIES OF GASES
Gases may be described in several ways.

Gases expand to fill and assume the shapes of their

containers.
They diffuse into one another.

They mix in all proportions.

Gaseous mixtures are homogeneous solutions.
Individual particles of a gas are invisible.
Some gases are colored:
Chlorine: greenish yellow
Bromine: brownish red
Iodine: violet
Some gases are combustible: hydrogen, methane
Some gases are chemically inert: helium, neon

Four fundemental properties determine the physical behavior of a

gas:

Pressure (P)
Volume of gas (V)
Temperature (T)
Amount of gas (n)

If we know any three of these properties, we can usually calculate

the value of the remaining one.
Units of Pressure
Pressure Units

Abbreviation

Atmosphere
Millimeter of mercury
Torr
Pound per square
inch
Kilogram per square
centimeter
Newton per square
meter
Pascal
Kilopascal
bar
millibar

Atm
mmHg
torr
lb/in2
kg/cm2

Equivalent to Standard
atmospheric pressure
1.0 Atm
760 mmHg
760 torr
14.696 lb/in2
1.0333 kg/cm2

N/m2

101,325 N/m2

Pa
kPa
bar
mb

101,325
101,325
1.01325
1013.25

Pressure
Pressure: force exerted per unit area

Pa
Pa
bar
mb

P=F/A

(unit: Pascal)

1 Pascal: a pressure of 1 N m
1 Pa = 1 N / 1 m2 = 1 N m -2

-2

103 Pa = 1 kPa
106 Pa = 1 MPa
1 bar = 105 N m

-2

= 105 Pa

1 bar = 102 kPa

1 bar = 0.1 MPa
P=F/A
m=V
P=V/A

= hA/A

P=h

Example: 1 mmHg pressure in Pascal units,

P=h
P = 0.1 cm (13.6 g /cm3) = 1.36 g /cm2
P = 1.36 g /cm2 . (1 kg / 103 g ). (104 cm2 / 1m2 ). (9.81 N /1 kg )
P = 133.4 N / m2
1 mmHg (1 torr) = 133.4 Pa
1 atm = 76.0 cm (13.6 g /cm3)
1 atm = 1.0336 kg/ cm2 (at)
1 atm = 1.0336 (9.81) 104 = 1.013 105 N / m2

1 atm = 1.013 105 Pa

1 atm = 1.013 102 kPa
1 atm = 0.1013 MPa
1 at = 1.0 kg/cm2 (9.81 m/s2) = 9.81 N/cm2
1 at = 9.81 N/cm2 (10000 cm2 / 1 m2) = 98.1 kPa
1 psi = 1 lbf / 1in2 = 0.454 kg /(2.54)2 = 0.0703 at
1 psi = 0.0703 at (98.1 kPa/ 1 at) = 6.996 kPa
Measurement of Gas Pressure: mercury barometer

The Simple Gas Laws

Boyle-Mariotte Law:
Independent experimental studies by the following scientists:

Robert Boyle (1627-1691) 1662

E. Mariotte (1620-1684)
1676

For a fixed amount of gas at constant temperature, the gas volume

is inversely proportional to the gas pressure.
P1V1 = P2V2 = constant

(constant T , n)

Isotherms: constant temperature curves

Charles and Gay-Lussac Law-1:

Charles (1746-1832)
Gay-Lussac (1778-1850)
The volume of a fixed amount gas at constant pressure is directly
proportional to the absolute temperature.

Isobars: constant pressure curves

When we change the temperature of an ideal gas by 1 C, volume
increases by 1/273 of its initial value.
V1 /T1 = V2 /T2 = constant
Charles and Gay-Lussac Law-2:
The pressure of a fixed amount gas at constant volumeis directly
proportional to the absolute temperature.
Isocors: constant volume curves
When we change the temperature of an ideal gas by
pressure increases by 1/273 of its initial value.

1 C,

P1 /T1 = P2 /T2 = constant

Avogadros Law:
Equal numbers-equal volumes
Equal volumes of different gases compared at the same
temperature and pressure contain equal numbers of molecules.
Equal numbers of molecules of different gases compared at the
same temperature and pressure occupy equal volumes.
At a fixed temperature and pressure, the volume of a gas is
directly proportional to the amount of gas.
V1 /n1 = V2 /n2 = constant

IDEAL GAS EQUATION:

v = f(T,p,n)

p1v1/n1T1= p2v2/n2T2 =..= pv/nT = CONSTANT =R

pv= nRT
pV=RT
n= m/M = N/L = v/V
N= number of molecules
L=Avogadro constant
V= molar volume
v= volume
Boltzman Constant=

k = R/L

pv=N/L RT = NkT
ideal gas constant
R = 8.3143 J/K.mol = 1.9872 cal/K.mol = 0.082056 lt.atm/ mol.K
= 0.08314 bar.dm3/ mol.K

IDEAL GAS MIXTURES

MXTURE:

n1, n2, n3, ni

p1, p2, p3, pi partial pressures of components
v1, v2, v3, vi

partial volumes

ideal gas equation for the mixture

pv =nRT
ideal gas equation for the components in the mixture
piv =niRT
pvi =niRT
Mol fraction

yi = ni /n

= vi /v

= pi / p

 yi = 1
mol fraction = volume fraction = pressure fraction

Daltons Law of partial pressures:

pi =pyi
pi = pyi = p yi =p

(yi, T, v =constant)

Amagats Law of partial volumes:

vi =vyi
vi = vyi = v yi =v

(yi, T, p =sabit)

Average molar weight of ideal gas mixtures:

M =m/n = RT /p = yi Mi
Average density of ideal gas mixtures:
= m/v = yi i
STANDARD CONDITIONS OF TEMPERATURE AND PRESSURE
Gas properties depend on temperature and pressure.
It is useful to work at a particular temperature and pressure.
The standard temperature for gases is defined as 0 C= 273.15 K
The standard pressure is 1 atm=760 mmHg
Standard conditions are usually abbreviated as STP.
KINETIC MOLECULAR THEORY OF GASES
Boyle, Gay-Lussac, Avogadro experiments,
Studies done by:
Bernoulli
Joule
Clausius
Maxwell
Boltzman

According to this model,

A gas is comprised of a very large number of

extremely small particles (molecules or in some
cases atoms) in constant, random, straight-line
motion.

Molecules of a gas are sepatated by

distances. The gas is mostly empty space.

Molecules frequently collide with one another and

with the walls of their container. However, these
collisions ocur very rapidly and most of the timr
molecules are not colliding.

These are assumed to be no forces beween

molecules (intermolecular forces) except very
briefly during collisions. That is, each molecule
acts independentlyof all the others, unaffected by
their presence.

Individual molecules may gain or lose energy as a

result of collisions: however, in a collection of
molecules at constant temperature, the total
energy remains constant.

great

SOME RESULTS OF KINETIC GAS THEORY

Macropcopic properties are related with microscopic properties.
Pressure
P = f/A

P = (1/3) mN v2
N = L/V
v2
m

(number of molecules per unit volume)

average value of the square of velocity for L molecules

mass of molecule

v = velocity of molecule
velocity components for the molecule in x, y, z directions,
X = dx / dt
Y = dy / dt
Z = dz / dt
V : molecule velocity,
V2 = x2 + y2 + z2
average value of the square of velocity for L molecules
<V2> = ( V12 + V22 + + VL2 ) / L
Taking the square root,
<V2>

1/2

Energy and Temperature

Pv = (1/3) Lm v2 = RT

E = (1/2) Lm v2
T = (2/3 R) E = (1/3 k) m v2
Grahams Law of Diffusion
Graham 1828-1848

Ayn koullarda eit hacimli gazlarn ok kk bir delikten geme

hzlarnn younluklarnn karekk ile ters orantl olduu ortaya
kmtr.
Gazlarn kk deliklerden yaynrln gsteren bu olaya efzyon
denir.
Ayn koullarda bulunan gazlar iin younluklar oran molar
ktlelerinin oranna eit olduundan ve yaynrlk hz yaynrlk
sresi ile ters orantl olduundan
r velocity of diffusion
t time of diffusion
Effusion refers to the passage of gas molecules through a tiny
opening in their container into an evacuated space.
Diffusion refers to the mixing of gases with one another. Each gas
spreads throughout the mixture until its partial pressure is the
same everywhere.
Grahams Law
r2/r1 = t1/t2 = ( 1/ 2)1/2 = (M1/M2)1/2

From kinetic theory,

Pv = (1/3) Lm v2 = RT
ortalama molar kinetik enerji ile termal enerji arasndaki bant
aadaki gibi yazlabilir:
E = (1/2) Lm v2 = (1/2) M v2 = 3/2 RT
MAXWELL-BOLTZMAN ENERGY AND VELOCITY DISTRIBUTION
N: gaz iindeki molekl says
E: gazn toplam enerjisi

E / N : molekl bana den ortalama enerji

Ni : molekl says
i : enerji miktar
Total energy : E = Ni i
Energy distribution:
T scaklnda bir gaz iinde enerjisi

bulunan molekllerin kesrini veren bant

ve + d

arasnda

ve v + dv

arasnda

Velocity distribution:
T scaklnda bir gaz iinde hz
v
bulunan molekllerin kesrini veren bant

T scaklnda bir gaz iindeki molekllerin boyutlu hareketi gz

nne alnarak Maxwell-Boltzmann enerji dalm

dN
2
1/ 2

N
( k T )3 / 2

1/ 2

e / kT d

T scaklnda bir gaz iindeki molekllerin boyutlu hareketi gz

nne alnarak Maxwell-Boltzmann hz dalm

dN
4
N

2 k T

3/ 2

v2

e (1 / 2 )) mv

/ kT

dv

Molecular Speeds

Root-mean-square Speed (Hz kareleri ortalamasnn karekk)

v2 1/2

 v2 1/2 =(3RT/M)1/2 = (3kT/m)1/2 = (3pV/M)1/2 = (3p/)1/2

(Hz kareleri ortalamas):

v2

v2 = 3kT/m
Average speed (Ortalama hz): v
v = (8kT/m)1/2 = (8RT/M)1/2 = (8pV/M)1/2 =
= (8p/)1/2

Most probable speed (En olas hz): Ve

Maxwell-Boltzmann hz dalm erisinin maksimumuna karlk
gelen deer
Ve = (2kT/m)1/2 = (2RT/M)1/2 = (2pV/M)1/2 =
= (2p/)1/2
En olas hz dier iki hzdan daha kk
Relation between the speeds (Molekl hzlar arasndaki bant):

v2 1/2 : v : Ve = (3)1/2 : (3/)1/2 : (2)1/2

BASIC RESULTS
Number of Collisions (arpma says)

Hareket
halindeki
molekln
molekllere arpma says

durduklar

varsaylan

dier

Z1 = (2) 2 v N
N: gazn birim hacimdeki molekl says
: molekl ap
Number of Collisions
Ayn cins molekller iin birim hacimde bir saniyede olan arpma
says
Z11 = (2 /2) 2 v N N
For different molecules,
Z12 = 212 v N1 N2 = [( 1 + 2)/2] (8kT/)1/2 N1 N2
12 : molekl aplarnn aritmetik ortalamas
: indirgenmi ktle
1/ = (1/m1) + (1/m2)

Serbest yol:
molekllerin ard ardna olan iki arpma arasnda aldklar yol
Ortalama Serbest yol:
molekllerin her iki arpma arasnda farkl uzunluklarda olan
serbest yollarn aritmetik ortalamas
= v / Z1 = v / [(2) 2 v N ] = 1 / [(2) 2 N ]
Molekllerin bulunduklar kabn yzeyine arpma says
Z = (1/4) N v At
Gazlarn difzyonu
Bir gaz molekllerinin bir baka gaz moleklleri arasna, bir sv
veya bir kat iine yaynmasna difzyon denir.
D = (1/3) v

 X2 = 2Dt

Fick yasas

D: difzyon katsays
t: sre
Gazlarn viskozitesi
Viskozite: Akkanlarn akmaya kar gsterdikleri diren
= (1/3) v
Gazlarn termal iletkenlikleri
q = k A (dT/dz)t
k = cv

Newton Yasas

Fourier Yasas

Termal iletkenlik

Nonideal Gases (Real Gases)

The van der Waals Equation:

n2 a

V 2

n b n R T

where a,b are van der Waals constants

2.LIQUIDS
STATES OF MATTER
Phase: physically and chemically homogeneous regions in a
system
Phases in a system , , ,
Solid phase k
Liquid phase s
Gaseous phase g
Vapor:
They behave like a gas, but they are the fluids that can be
liquified by the effect of pressure at the temperature they
exist
Critical temperature: the temperature at the critical point
Critical pressure: the pressure at the critical point
Critical point: the highest temperature-pressure point on a
vapor pressure curve and represents the highest temperature
at which the liquid can exist

Plasma phase: 4th state of matter. At very high

temperatures, a mixture of gas molecules, atoms, ions and
elecrons
THERMODYNAMICS OF PHASE TRANSITIONS FOR PURE
SUBSTANCES
(SAF
MADDELERDE
FAZ
DNMLERNN
TERMODNAM)
Variation of Vapor Pressure with Temperature
Log P = - A / T
Emprical relation

+C

(August, 1828)

CLAUSIUS-CLAPEYRON EQUATION
dP
S ks
H ks

dT Vs Vk
T (Vs Vk )

Liquid-vapor equilibrium
dP
S sb
H sb

dT Vb Vs
T (Vb Vs )

dP

dT

d ln P

dT

H sb
H sb

P
T ( RT / P )
RT 2

H sb
RT 2

Clausius-Clapeyron equation

Solid- vapor equilibrium

dP
S kb
H kb

dT Vb Vk
T (Vb Vk )

dP

dT

d ln P

dT

H kb
H kb
H kb

P
T Vb
T ( RT / P)
RT 2

H kb
RT 2

Clausius-Clapeyron equation

Troutons Rule: For most of the liquids, Enthalpy

vaporization divided by the normal boiling point,
Hb
88 JK-1mol-1
Tb

This relation is valid for non-polar liquids.

It is not valid for liquids containing hydrogen bonds.

of

PHYSICAL PROPERTIES OF MATTER

Viscosity () : resistance of fluid to flow
()

: inverse of viscosity (ability to flow)

=1/

3.SOLUTIONS
CONCENTRATION
The concentration of a solute in solution can be expressed in
several different ways.

1. Percentage by mass: The percentage by mass of a

solute in a solution is 100 times the mass of the
solute divided by the total mass of the solution.

2. Mole fraction: The mole fraction of a component of a

solution is the ratio of the number of moles of that
component to the total number of moles of that
substances present in the solution
xi = ni/n = (mi/Mi )(mi/Mi )
xi = 1
3. Molarity: The molarity of a solution is the number of
moles of solute per liter of solution.
M(mol/L) = (n2/ v ) = ( m2/M2 ) /v

4. Molality: The molality of a solution is the number of

moles of solute dissolved in 1 kg of solvent.
m ( mol/kg ) = n2 /m1 = ( m2/M2 ) / m1
5. Normality: The normality of a solution is the number
of equivalent weighs per liter of solution.

HENRYS-RAOULTS-DALTONS LAWS
Henrys, Raoults ve Daltons Laws

To determine the components in the liquid and vapor phases

for mixtures at equilibrium at certain pressure and temperature
conditions
Pure liquids are at equilibrium with their vapors at certain
temperature and pressure.
Liquid mixtures are also at equilibrium with their vapors at
certain temperature and pressure.
The vapor phase of a Water-sugar mixture contains one
component. Sugar does not vaporise.
Henrys Law
The solubility of gas in liquid depends on :
o temperature
o partial pressure of gas
o nature of solvent
o nature of gas
pi =xiKi

Henrys Law

In this equation,
Ki : Henry constant
pi : partial pressure of i-component
p0 : Standart pressure( generally 1 atm. )
pi (partial pressure in the vapor phase) is directly
proportional with xi (mol fraction in the liquid phase).
Very dilute solutions obey Henrys Law.

Solubility of gases in liquids are expressed as Henrys

constants.
Raoults Law
For ideal solutions
For pure liquids in equilibrium with their vapors:
xi =1
pi =pi0
pi0 = vapor pressure of pure i-component at a given temperature.
Ideal mixtures:
pi =xi pio

Raoults Law

Daltons Law
pi = pi0 =pT* yi
The relation between the Partial pressure (pi ) in the vapor phase
and mol fraction in the vapor phase ( yi) and the total pressure
(pT) for a mixture
For Daltons Law,
pT = p1 + p2 + ..pi = sum of the partial pressures of
components =total pressure

COLLIGATIVE PROPERTIES (SAYISAL ZELLKLER)

The properties of solutions that depend principally upon the

concentration of dissolved particles, rather than upon the
nature of these particles.
(deal zeltilerde znen maddenin tanecik byklne,
ekline, cinsine, kimyasal yapsna ve ykne bal olmayp
yalnzca saysna(miktarna=mol saysna=molekl saysna)
bal olan zelliklere Saysal zellik denir) :

Lowering of vapor pressure

Freezing point depression (Donma scakl dmesi)

Boling point elevation (Kaynama scakl ykselmesi)

Osmosis (ozmoz olay)

Lowering of vapor pressure

(Buhar Basnc Dmesi):

Raoults law for a 2 component mixture :

0

p p1 p 2 p1 x1 p 2 x 2 p1 x1 p1 (1 x 2 ) p1 p1 p1 x 2 p1
0

p1 p1 p1 x 2
0

p1 p1
p1

p
p1

x2

Solute: not vaporizable

Vapor pressure of pure solvent ( p1 )

Partial vapor pressure of solvent in solution ( p1 )
p lowering

of vapor pressure

p
p1

lowering of vapor pressure due to pure solvent

For molecular substances,

m2

M 2
n2
p

x2

0
n1 n2 m1 m2
p1

M1 M 2

2. Freezing point depression (Donma scakl Dmesi):

Solid-liquid equilibrium temperature: Freezing point
At constant pressure, freezing point of solvent in a solution (T)
is lower than the freezing point of pure solvent (T 0) .
Example: 00C de soutulan saf sudan buz ayrlmaya balad
halde tuzlu su henz donmaya balamamtr.
Solid(1)

( 1, k 1, s )
0

ln x1

Liquid(1)

RT

G1
sabit
RT

( T,p constant)

G1 : Molar Gibbs free enthalpy for melting (pure solvent)

H 1 : Molar enthalpy for melting (pure solvent)

V1 : difference in molar volume during melting (pure solvent)

kat

x2

Mole fraction of solvent in solution changes from 1 to x

then

freezing point temperature changes from T0 to T.

x1

d ln x1
1

ln x1

H 1 T dT
R T0 T 2

H 1 T T0

R TT0

T and T0 are close to each other, so TT0 = T02

Td T0 T
Td : difference between the freezing points

For ideal dilute solutions,

x2 is small, so:

ln x1 = ln(1 x 2 ) x 2

Replacing,

RT0 2
x2
Td

H
1

(In dilute solutions, number of moles of solute can be neglected

as compared to the number of moles of solvent) :

n2
n2
x 2 n1 n2
n

1 M1
n2
n2
m
m1
m1
x 2 mM 1

Freezing point depression equation:

RT0 2 M 1
n
m2
m Kd m Kd 2 Kd
Td

m1
M 2 m1
H 1
Kd (Freezing point depression constant=Kriyoskopy constant)

Kriyoskopy constants for some solvents

Solvent

Kd ( K.kg/mol)

water

1.86

Benzene

5.07

CCl4

29.80

Kafur

40.0

If the temperature difference is too small, large K d value solvents

are preferred.
Kriyoskopy method is used to find the molecular weight of
substances.
3. Boiling point elevation (Kaynama Noktas Ykselmesi)
Boiling Point: the temperature at which the solvent is in
equilibrium with its vapor.
G1 : Molar vaporization free enthalpy of pure solvent

H 1 : Molar vaporization enthalpy of pure solvent

V1 : difference in volume during evaporation

Mol fraction of solvent in solution changes from 1 to x

boiling point changes from T0 to T .
x1

H 1 T dT
1 d ln x1 R T T 2
0

ln x1

H 1 T T0

R TT0

, then

T and T0 are close to each other.

TT0 = T02
Tb T0 T

Tb difference in boilng points

For ideal dilute solutions,

x2 is very small, so:

ln x1 = ln(1 x 2 ) x 2

Replacing,

RT0 2
x2
Tb

H
1

(Seyreltik zeltilerde znenin mol says zcnn mol

says yannda ihmal edilebilecek byklktedirJ

n2
n2
x 2 n1 n2
n

1 M1
n2
n2
m
m1
m1
x 2 mM 1

Equation for boiling point elevation:

RT0 2 M 1
n
m2
m Kbm Kb 2 Kd
Tb

m1
M 2 m1
H 1
Kb (boiling point elevation constant=Ebulioskopy constant)
Ebilioskopy constants for some solvents
Solvent
water
Benzene

Kb ( K.kg/mol)
0.503
2.64

CCl4

4.88

Kafur

6.09

Ebulioskopy is used to find the molecular weights of solutions.

4. Osmotic pressure (Osmotik basn)

p1
P, T constant

p1 p1

solvent

p1 p1
0

0
h

solution

Bir membranla birbirlerinden ayrlm zc molekllerinin saf

zcden zeltiye doru kendiliinden gemesine Ozmoz
denir.

Bu durumda zeltinin hacmi artar. zelti tarafndaki bu hacim

art, zelti tarafndaki ince bir boru ile takip edilmektedir.
Denge durumunda ince klcal boruda seviye h kadar bir
ykseklie ularken zc geii durur.
Denge kurulduktan sonra ince borudaki h yksekliindeki
svnn zelti zerine uygulad hidrostatik basnca Ozmotik
basn denir.
Ozmotik basn ==gh
Ozmotik bas forml :

RT p1 0

ln

V1 p

According to Raoults law:

For dilute solutions:

p1
p1

x1 (1 x 2 )

ln x1 ln(1 x 2 ) x 2

RT
RT
RT
ln x1
ln(1 x 2 )
( x 2 )

V1
V1
V1
RT
V1

x 2

n2
n
2
n1 n2 n1

x2

RT n2

V1 n1

n1V1 : v total volume of solution (znenin hacmi ihmal)

n2

RT cRT

n2
: hacim birimi L olmak koulu ile zeltinin molaritesi
v

Example: Suyun 1 atm.basntaki erime entalpisi (He) ve

Buharlama entalpileri (Hb)
He=322.7 J/g
Hb =2253 J/g
200C deki buhar basnc ise p su 17.363 mmHg dr. 9 .00 g renin
100 g suda znmesi ile hazrlanan zeltinin:
i.

200C deki buhar basnc dmesini

ii.

Ozmotik basnc

iii.

Donma scakl dmesini

iv.

Kaynama scakl ykselmesini bulunuz?

i.

Buhar basnc dmesi:

p p su pre p su p1 p1 0 x1

n re

9.00
0.15
60.00

n su

100
5.55
18

x1

5.55
0.974
5.55 0.15

x 2 0.026

Molalite?
100 g

su

9.0 g reyi zerse

1000 g su

x2

1000 * 9.0
90 g re zer
100

Molalite=

90
= 1.5 mol/kg
60

x2

kadar re zer

p1 p1 x1 17.363 * 0.974 16.911mmHg

0

p p1 p1 17.363 16.911 0.452mmHg

ii.

Donma noktas dmesi:

2

K d RT0 M 1

8.314( J / K .mol ) * (273.2) 2 ( K 2 ) M 1 ( g )

1

1922 K .g / mol
322.7 J M 1 ( g )
H e
*
g
1mol

=1.922 K.kg/mol
Td T0 T K d * m 1.92 * 1.5 2.88 K

iii.

Kaynama noktas ykselmesi

2

Kk

RT0 M 1 8.314( J / K .mol ) * (373.2) 2 ( K 2 ) M 1 ( g )

513K .g / mol
2253 J M 1 ( g )
H b
g
1mol
=513 K.kg/mol

Tk T T0 K k * m 0.513 * 1.5 0.765 K

iv.

Ozmotik basn
0

RT p1
8.314( J / K .mol ) * 293.2 K 17.363
ln

ln
35.72 * 10 5 Pa
6
3
V1
p1
16.911
18 * 10 m

101325 Pa=1 atm

1.033 bar=1 atm
1033 mbar=1 atm
Yerlerine konularak istenilen birime evrilir.

CHEMICAL KINETICS
Chemical Kinetics: reaction rates and mechanisms.

In a chemical reaction,
Change with respect to time,
Reaction stages,
Factors affecting reaction rate
Chemical Thermodynamics: equilibrium

Reaction Rate:
species

Change in concentration per unit time of any

Catalyst: affects reaction rate

Catalysis: phenomena affecting reaction rate
Reaction Rate
C: concentration at any time t of reacting species
X: concentration at any time t of any product formed

dC
dt

(-) concentration of reactants decrease with time

dX
dt

(+) concentration of products increase with time

A P

reaction,

vA

d A
dt

vP

d P
dt

In General,
aA + bB cC + dD

RH =

1 d A
1 d B
=
=
a dt
b dt

1 d C
=
c dt

1 d D
d dt

rnek: For reaction A P , find the reaction rate if 2.4

mol L-1 P is formed in 20 minutes. (mol L-1s-1).

2.4

3
RH = ( 20)(60) 2 10
mol L-1s-1

Units of Reaction Rate

: mol L-1s-1
Units of Concentration:

mol L-1, mol cm-3, molecules cm-3,

mol m-3

Units of time: second, minute, hour, day, year

For gaseous phase reactions: pressure time-1
Example:
2 HI (g) H2 (g) + I2 (g)
Fort the reaction above, I2 concentration change with time is
1.5x10-5 mol L-1s-1.
Find the reaction rate, reaction rate of HI and H 2.

RH =

1 d H2
=
1 dt

1 d I2
1 d HI
=
= 1.5x10-5 mol L-1s-1
2 dt
1 dt

d HI
= 2 x 1.5x10-5 = 3.0 x 10-5 mol L-1s-1
dt

Factors affecting reaction rate,

Nature of reacting species

Concentration of reactants
Temperaure
Catalyst

Reaction Order
aA + bB cC + dD
RH = k A a B b
k = reaction rate constant
a = reaction order with respect to A
b = reaction order with respect to B
n = a + b = total reaction order

RH = k A 1

1.order

RH = k

0. order

RH = k A 2

2. order

Reaction Rate Constant

RH = k A n
k = Reaction Rate Constant

RH

A n
RH

A n

mol L1 s 1
= mol1-n Ln-1 s-1
1
n
mol L

Half Life:
Time at which the initial concentration is half of the initial
value ( 1/2)
t=0

C = C0

t = 1/2

C = C0/2

Effect of temperature of Reaction Rate

Vant Hoff (1887) relation
log k B

A'
T

Arrhenius (1889) relation

d ln K c
E

dT
RT 2

Kc : equilibrium constant

E : change in internal energy

Arrhenius relation

k Ae

Ea / RT

A: Arrhenius constant (frequency factor)

E: reaction activation energy

ln k ln A

Ea
RT

log k log A

Ea
2.303 RT

2. EVALUATION OF KINETIC DATA

Differential Method
1st order
A P (tek basamakl reaksiyon)
RH =

d A
= k A
dt

Reaksiyonun ilerlemesi esnasnda, tye gre A konsantrasyonu

izlenerek,
A - t deiimi grafii izilir.
Eri zerinde, eitli noktalardan izilen teetlerin eimi,
reaksiyon hzna eit olacaktr.
Reaksiyon hz sabiti,
k=

A 1
t A

Integral Method
Zeroth order Reaction
RH =

d A
= k A 0 = k
dt

d A
=k
dt

k=

A
t

d A = k dt

d A

dt

A =- kt + C

C= integral cst

Initial condition, t =0, A =A 0

A = - kt +A 0
Half life:
t= 1/2 iken A =A 0 /2
1/2 = A 0 /2k

1st Order Reaction

RH =

d A
= k A 1 = k A
dt

d A
= k A
dt

A 1
A

k= t
d A
A

= k dt

d A

kd t

Ln A = - kt + C

C= integral cst

Initial condition, t =0, A =A 0

Ln A = - kt +ln A 0
LogA = - kt/2.303 +LogA 0

Half life:
t= 1/2 iken A =A 0 /2
Ln (A 0/2) = - k 1/2 +ln A 0
1/2 = 0.693 /k

2nd Order Reaction

RH =

d A
= k A 2 = k A 2
dt

d A
= k A 2
dt

d A

= k dt

A 2

d A

kd t
kt C

C= integral cst

Initial condition, t =0 , A =A 0

1
1
kt
A
A 0

Half life:
t= 1/2 A =A 0 /2
1
1
k 1/ 2
A
A 0 / 2

1/2 = 1 /(kA 0)

CHEMICAL EQUILIBRIUM
When equilibrium is reached,
Forward reaction rate = reverse reaction rate

Reactants

Products

Ke : equilibrium constant
Le Chtelier Law
Parameters affecting chemical equilibrium:

Change of Concentration

Change of volume

Change of pressure

Temperature

Addition of a Catalyst

Upon change one of these parameters, then the equibrium is shift

and re-established.

Homogeneous Chemical Equilibrium for Ideal Gaseous Mixtures

n A A( gas ) n B B ( gas ) ... nC C ( gas ) n D D( gas ) ...

( pC / p 0 ) C ( p D / p 0 ) D
G G RT ln
( p A / p 0 ) A ( p B / p 0 ) B
0

G G 0 RT ln K p

G 0 RT ln K p

Kp

equilibrium constant for partial pressures

Kc

equilibrium constant for concentration

Kx

equilibrium constant for mole fractions

RTc 0
K p K c
0
p

Kp=Kx(p/p0)n
For n=0
Kp=Kx=Kc
Temperature Dependence of Equilibrium Constant
ln K p

G 0
H 0 S 0

RT
RT
R

H 0
d ln K p / dT
RT 2

vant Hoff equation

d ln K x / dT

H 0
RT 2

ln K p ln K c n ln R n ln T

Heterogeneous Chemical Equilibrium

More than one phase (solid, liquid, gas)
n A A( s ) n B B ( g ) ... nC C (l ) n D D( g ) ...

G G RT ln
0

..( p Z A / p 0 )

( p B / p 0 ) B

G G 0 RT ln K p

G 0 RT ln K p
K K K p

CHEMICAL THERMODYNAMICS
TERMODNAMK: snn ie dntrlmesi, enerji elde edilmesi
almalar
Fiziksel ve kimyasal olaylardaki denge
Eneri alverileri
Olaylarn kendiliinden olma eilimi
Olaylarn Yn
TERMODNAMK YASALARI
1.
2.
3.
4.

Sfrnc Yasa : termal denge

Birinci Yasa : snn ie evrilmesi
kinci Yasa: snn ie evrilmesi verimi
nc Yasa: entropinin mutlak deerinin tanmlanmas

U i enerji
H entalpi
S entropi
T mutlak scaklk
A Helmoltz enerjisi (serbest i enerji): sabit hacim altnda yryen
olaylar
G Gibbs enerjisi (serbest entalpi): sabit basn altnda yryen
olaylar
TERMODNAMN BRNC YASASI
(ENERJNN KORUNUMU)
Enerji yoktan var edilemez, var olan enerji yok edilemez. Bir
halden dier hale dntrlebilir.

Isnn tamam ie dntrlemez.

Evrenin enerjisi sabittir.
ENERJ: bir sistemin i yapabilme kapasitesi
yapan sistemin enerjisi azalr
alan sistemin enerjisi artar
Is veren sistemin enerjisi azalr
Is alan sistemin enerjisi artar
Is: sistem ile ortam arasndaki scaklk farkndan doan enerji
: sistem ile ortam arasndaki basn farkndan doan enerji
Enerji trleri: s, elektrik, mekanik enerji
Elektrik
enerjisi:
santralarda retilir

termoelektrik,

nkleer,

ve

hidroelektrik

Pil: kimyasal enerjiyi elektrik enerjisine evirir

Yakt hcreleri: byk enerji
POTANSYEL ENERJ:
Bir sistemin konumundan dolay kazand enerji
m: ktle
g: yerekimi ivmesi
F= mg
Z yksekliindeki sistemin potansiyel enerjisi
Ep = Fdz = mg dz = mgz
Gerilmi veya sktrlm bir yay zerine uygulanan kuvvet:
Fyay = kz
k: Hook sabiti
z: yayn uzunluu
Potansiyel enerjisi:
Eyay = Fdz = k zdz = kz2

KNETK ENERJ:
Ktlesi m
Hz z= dz/dt
vmesi z =dz/dt = d2z/dt2
Olan sistemin momentumu mz
Momentumun zamanla deime hz olan kuvvet
Fz = d(mz)/dt = m(dz/dt) = mz olarak tanmlanr.
Kinetik enerji
Ek = Fzdz = m (dz/dt) dz = m (dz/dt) dz = m zdz = m z2
ELEKTRK ENERJS
Ee = Q = lt = RI2t
R = /l
R: diren
: potansiyel fark
I: akm iddeti
t: sre
Ee : elektrik enerjisi
Q: devreden geen toplam yk

ENERJ
Bir sistemi oluturan atom, iyon, molekl gibi en kk yap
talarnn sahip olduu tm enerjilerin toplam
U = 1 mol i enerji
u = n mol i enerji
u = nU
Bir sistemin i enerjisi
u = u0 + utit + udn + ute + uelek + uek
u0 = mc2

sistemin ktlesine karlk gelen durgun enerji

 enerjinin mutlak deeri belirlenemez.

Fiziksel ve kimyasal olaylar srasndaki
llebilir.

enerji

deiimi

Bir piston ierisine sktrlm bir ideal gazdan oluan bir sistem
dnelim.
Sisteme gele i ve s alverileri
+
Sistemden giden i ve s alverileri Sistem ve ortam arasndaki s ve i alverierinin toplam,
u=q+w
Termodinamiin Birinci Yasas,
du = q +w
u = hal fonksiyonu
q, w = yol fonksiyonu

u2

u1

du

q
0

w
0

u2 u1 = u = q + w
evrim boyunca Termodinamiin Birinci Yasas,

du q w 0

= evrim boyunca integral ilemcisi

trleri
Ortama akan diferansiyel i
w = Fdz
ortama verilen i +
sistemden ortama akan i

Sistemden ortama akan i

w = - Fdz
Gazn ortama yapt diferansiyel i (Sistemin ortama yapt i):
w = - Fdz = - port Adz = - port dv
Tersinir ve tersinmez olaylarda i:
w = - port dv

tr

-pdv

T2

qv = u = n U = n

( a + bT + cT2 + ) dT

T1

Entalpi Fonksiyonu, Cp snma ss

Sabit basntaki molar snma ss
Sabit basnta

dp = 0

d(pv) = pdv + vdp = pdv

qp = du - w = du (-pdv) = du + d(pv) = d(u + pv) = dh
Entalpi,
h u + pv
kapasite zellii
H U + pV
iddet zellii
evrim boyunca,

dh = 0

H = U + pV = U + RT

dH = dU + R dT
Cp dT = Cv dT + R dT
Cp Cv = R
zotermik Tersinmez lemler
alverii
w = - port (v2 v1)
zotermik Tersinir lemler
alverii

w = - port dv

tr

id

-pdv -(nRT/v) dv

V2

w = -nRT

dV
V
V
V
nRT ln 2 p1 v1 ln 2 p2 v2 ln 2
V1
V1
V1
V1 V

Scaklk sabit olduu zaman ,

u = 0
h = 0
Termodinamiin 1. Yasasna gre,

q = -w

Adyabatik ilem
Is aknn olmad sistem
Termodinamiin 1. Yasasna gre,
du = q + w = 0 + w = w = - port dv

w = du = nCv dT
Bu 2 eitliin birletirilmesiyle,
nCv dT = - port dv

tr

id

nCv dT - port dv - (nRT/v) dv

dT
R dv

T
Cv v

R
1
Cv

ln

T2
V
( 1) ln 2
T1
V1

V2

dV
V
V
V
nRT ln 2 p1 v1 ln 2 p2 v2 ln 2
V1
V1
V1
V1 V

T2
V
( 1 ) 1
T1
V2

T2
p
( 2 ) 1 /
T1
p1

p1v1 = p2v2

deal Gazlarda Basn-Hacim ilikisi

Pvm = k
TERMODNAMN KNC YASASI

1. Scakl her tarafnda ayn olan bir s deposundan s alarak

darya i vermek zere srekli olarak alan bir makine
yaplamaz. Byle bir makinann yaplabilmesi iin farkl
scaklkta ikinci bir s deposuna gerek vardr.
2. Verim: makinedan alnan iin mutlak deerinin makineya
gelen snn mutlak deerine oran
Verim daima 1den kktr.
3. Scak depodan alnan snn bir evrim ile ie dntrlmesi
ayn zamanda scak depodan souk depoya s aktarm
olmadan imkanszdr (i makinas) (Max Planck).
4. Souk bir depodan scak bir depoya s aktarm ayn
zamanda
belli
miktardaki
ii
sya
dntrmeden
imkanszdr (s pompas) (Rudolf Clausius).

CARNOT EVRM
Farkl scaklkta 2 s deposu ve 2 s deposu arasna yerletirilmi
bir i deposundan oluan tersinir olarak alan bir sistem.
4 basamakl bir evrim halinde alr:
1. ab basama: izoterm tesinir genleme
pava = pbvb T2 = sabit
2. bc basama: adyabatik tersinir genleme
pbvb= pcvc

T2 T1

3. cd basama: izoterm tersinir skma

pcvc = pdvd

T1 = sabit

4. da basama: adyabatik tersinir skma

pdvd = pava

T1 T2

T1 ve T2 scaklklar arasnda adyabatik tersinir genleme ve

skma iin,

T2
V
V
( c ) 1 = ( d )
T1
Vb
Va

Vb / Va = Vc / Vd
Basamaklardaki i alverileri,

w w = wab + wbc + wcd + wda

=

nRT2 ln

Vb
- n Cv (T2 T1) +
Va

nRT1 ln

Vb
+ n Cv (T2
Va

T1)
Sistemin yapt

= nR ( T2 T1 ) ln

sisteme yaplan

Vb
Va

q qab + qbc + qcd + qda = - wab + 0 - wcd + 0

Vb
Vb
- nRT1 ln
Va
Va
V
nR ( T2 T1 ) ln b
0
(Hal Fonksiyonu deil)
Va

nRT2 ln

Termodinamiin 1. Yasasndan,

du q w

nR ( T2 T1 ) ln

Vb
Va

nR ( T2 T1 ) ln

(Hal Fonksiyonu)
enerji

u = uab + ubc + ucd + uda

= 0 - n Cv (T1 T2) + 0 + n Cv (T2 T1) = 0

Vb
Va

= 0

Entalpi

h = hab + hbc + hcd + hda

= 0 - n Cp (T1 T2) + 0 + n Cp (T2 T1) = 0

evrim boyunca tersinir s alverilerinin scakla oran,

q tr q ab

T
T2

q tr

q cd
T1

q da
T

q2
0
q
0

1
T2
T
T1
T

q2
q
1
T2
T1

nR ln

qtr
T

q bc
T

Vb
Va

nR ln

Vb
Va

=0

Tam diferansiyel (Hal fonksiyonu)

ds

qtr
T

ENTROP (Clausius, 1854)

Termodinamiin 2. Yasas

ds

q tr
0
T

Termodinamiin 1. ve 2. yasalarndan,
du = qtr +wmax = Tds - pdv

du Tds pdv 0

w=-

pdv

Tds

Entropi deimeksizin yaplan ilemler = zentropik lem

Carnot evrimi= 2 izotermik + 2 izentropik ilem

du q w

ds

q1 + q 2 + w = 0

q1
q
q tr
2

T1
T2
T

= 0

(1.Yasa)
(2.Yasa)

Carnot Makinasnn Verimi ( )

w
q2

q2 q1
q2

n R (T2 T1 ) ln (vb / va )
T2 T1
T

=
T2
T2
n R T2 ln (vb / va

Termodinamik Scaklk
Termodinamik scaklk: - 273.15 C = 0 K (Kelvin Scakl,
mutlak sfr)
Rankine scakl : -459.67 F = 0 R
CLAUSIUS ETSZL
Bir
sistemdeki
Yasasndan,
dssis

Entropi

qtr
T

Tersinmez olaylarda,

deiimi

Termodinamiin

2.

ds sis

qtz
T

Bu 2 bantnn birletirilmesiyle, Clausius eitlii elde edilir,

dssis

qtr
T

Clausius eitlii

Ortamdaki entropi deiimi

ds ort

qort
qsis

T
T

Evrendeki entropi deiimi

dSevr = dSsis + dSort

dSevr = dSsis + dSort =

qsis
qort
qtr
qtr

0
T
T
T
T

Enerjisi sabit olan evrenin entropisi srekli artar.

Entropi: sistemin dzensizliinin bir ls

TERMODNAMN NC YASASI
MUTLAK ENTROP
Element ya da her trden bileiin saf
kristallerinin mutlak sfrdaki entropileri sfrdr.
(Nernst, 1906)
T 0,

S=0

(saf ve hatasz kristaller)

ve

hatasz

Mutlak sfrdaki deeri sfr olan entropinin herhangi bir

scaklktaki mutlak deeri
mutlak sfr ile bu scaklklar
arasndaki entropi artna eittir.

Entropinin Mutlak deerinin hesaplanmas

Mutlak sfrdan, herhangi bir T scaklna tersinir olarak
stlan 1 mol saf ve hatasz kristalin entropisindeki art, o
scaklktaki mutlak entropiye eit olur,
qtr
T

ds

C p dT
T

dS

= S S0 = S 0 = S

S0

Katlarn kristal dnm olmad srece, molar mutlak

entropileri,

S=

C p dT
T

rnein Cp = a T3

S=

C p dT
T

ise,

aT 3 dT
T

= a

2
T dT

a T1

TERMODNAMN TEMEL ETLKLER

Evrendeki entropi deiimi
dSevr = dSsis + dSort

dSevr = dSsis -

qsis
T

Cp
3

Serbest enerji fonksiyonu (Helmoltz enerjisi)

qv
T

dSevr = dS -

= dS -

dU
T

(v, T = sabit)

1. Hacim yannda, i enerjinin de sabit olduu olaylarda,

dSevr = (dS)v,u
2. Hacim yannda, entropinin de sabit olduu olaylarda,
dSevr = - (dU / T)v,s
3. Sabit hacim ve sabit scaklkta, i enerji ve entropi birlikte
deiiyorsa,

dSevr = dS -

dU
T

- T dSevr = dU TdS
Sabit scaklkta dT = 0
d(TS) = TdS + SdT = T dS
- T dSevr = dU d(TS) = d (U-TS)
A U TS

(v, T = sabit)

Serbest enerji fonksiyonu, Helmoltz enerjisi

- T dSevr = dA

(v, T = sabit)

dSevr 0, dA 0

olay kendiliinden yrr (Tersinmez)

dSevr = 0, dA = 0

olay dengede yrr (Tersinir)

dSevr 0, dA 0 olayn tersi kendiliinden yrr (Tersinmz)

Ayrca,

dA = dU TdS
dU 0, dS 0, dA 0
dU0, dS
(Tersinmz)
dU = TdS,

0,

olay kendiliinden yrr (Tersinmz)

dA 0

olayn tersi

kendiliinden yrr

dA = 0 olay dengede yrr (Tersinir)

dU 0, dS 0, dA 0 olay dk scaklklarda kendiliinden

yrr (tz)
dU0, dS 0, dA 0
olay yksek scaklklarda kendiliinden
yrr (tz)

Tersinir olaylar srasnda, sistemden ortama maksimum i ak

olur,
tr
-w max = - A
(v, T = sabit)

Serbest Entalpi fonksiyonu (Gibbs enerjisi)

dSevr = dS -

qp
T

= dS -

dH
T

(P, T = sabit)

1. Basn yannda, entalpinin de sabit olduu olaylarda,

dSevr = (dS)P,u
2. Basn yannda, entropinin de sabit olduu olaylarda,
dSevr = - (dH / T)P,s
3. Sabit basn ve sabit scaklkta, entalpi ve entropi birlikte
deiiyorsa,

dSevr = dS -

dH
T

- T dSevr = dH TdS
Sabit scaklkta dT = 0
d(TS) = TdS + SdT = T dS
- T dSevr = dH d(TS) = d (H-TS)
G H TS

(P, T = sabit)

Serbest Entalpi fonksiyonu, Gibbs enerjisi

- T dSevr = dG

(P, T = sabit)

dSevr 0, dG 0

olay kendiliinden yrr (Tersinmez)

dSevr = 0, dG = 0

olay dengede yrr (Tersinir)

dSevr 0, dG 0 olayn tersi kendiliinden yrr (Tersinmz)

Ayrca,
dG = dH TdS
dH 0, dS
(Tersinmz)
dH0, dS
(Tersinmz)
dH = TdS,

0,

0,

dG 0

dG 0

olay kendiliinden yrr

olayn tersi

kendiliinden yrr

dG = 0 olay dengede yrr (Tersinir)

dH 0, dS 0, dG 0 olay dk scaklklarda kendiliinden

yrr (tz)
dH0, dS 0, dG 0

 olay yksek scaklklarda kendiliinden

yrr (tz)

Tersinir olaylar srasnda, sistemden ortama maksimum i ak

olur,
tr
-w e,max = - G
(P, T = sabit)

KAPALI SSTEMLERN TEMEL TERMODNAMK DENKLEMLER

du = q + w (birinci yasa)
dS = qtr / T

(ikinci yasa)

H = U + PV
( U / T)v = Cv
( H / T)P = CP
A = U TS = G PV
G = H TS = A + PV
KAPALI
SSTEMLERDE
HAL
DEKENLERNE BALILII

FONKSYONLARININ

U = q + w
dU = qtr + wmak = TdS PdV
H = U + PV
dH = dU + PdV + VdP = TdS PdV + PdV + VdP = TdS + VdP
A = U TS
dA = dU TdS SdT = TdS PdV - TdS SdT = - SdT PdV

HAL

G = H TS
dG = dH TdS SdT = TdS + VdP - TdS SdT = - SdT + VdP

BLM-10

KMYASAL TERMODNAMK
10.1. Kimyasal Termodinamik tanm
Termodinamiin temel yasalarnn kimyasal olaylara uygulanmas ile ilgili ilemleri
kapsayan bilim dal Kimyasal Termodinamik olarak adlandrlr.
Kimyasal reaksiyonlar neticesinde baz olaylarla karlalr ve baz nicelikler tespit
edilir ve llr. Nedir bu nicelikler:
-

Hacim deiimi

enerji deiimi

Entalpi deiimi

Entropi deiimi

Serbest i enerji deiimi

Serbest entalpi deiimi

Tepkime oran

Denge sabiti

Kimyasal Termodinamikta; bahsi geen bu niceliklerin belirlenmesi yannda, bu

niceliklerin scaklk ve basnca ballklar fonksiyonel olarak belirlenir.
10.2 Termokimya
enerji deiimi, entalpi deiimi, s ve i alverileri nin termodinamiin birinci
yasasna gre irdelenmesi ile ilgili ilemler Termokimya bilim alan iinde gerekleir.
10.3. Tepkime konu() nedir
Tipik bir kimyasal reaksiyon iin genel ifade u ekildedir:
A A B B ... C C D D .....

A ve B bileenleri: reaksiyona girenler

C ve D bileenleri : reaksiyondan kan rnler
A , B .: Reaksiyona girenlerin stoikyometrik katsaylar

C , D : Reaksiyondan kanlarn stoikyometrik katsaylar

Byle tipik bir reaksiyonda yukarda sraladmz birtakm termodinamik niceliklerde

deimenin olmas mutlaktr. Bu niceliklerden herhangi biri iin F denilirse, reaksiyonun
dengedeki bir annda bu termodinamik nicelikteki deime F olarak ifade edilir:
F ( C FC D FD ....) ( A FA B FB ........)

Eitlik 10.3.2e gre yazlan bu eitlikte F termodinamik nicelii molar hacim,snma ss

,molar entropi mutlak deeri llebilen byklkler yannda molar i enerji,molar entalpi ve
serbest entalpi vb. deerleri olabilir.
Bir kimyasal reaksiyon iin birden fazla birim stoikyometrik denklem
yazlabilir.Yazlan kimyasal denklemde reaksiyona giren veya kan bileenlerden birisinin
stoikyometrik katsays 1 olacak ekilde yazlyorsa

bu denkleme Birim stoikyometrik

denklem denir .
Tepkime konu tanm olarak ifade edilirse:
Herhangi bir bileen iin ;Birim stoikyometrik katsay bana

mol

saysndaki deiim
0

rnein : ni : i-bileenin balangtaki mol says

ni : i-bileenin herhangi bir andaki mol says
0

( n ni )
= i
i

i-bileeni iin tepkime konu

Eitlik 2.1.1.2 ye gre tepkime konu:

0

( n n A ) ( n B n B ) ( nC nC )

........
= A
A
B
C
rnek soru: N 2 3H 2 2 NH 3 kimyasal reaksiyonun gz nne alarak;
10 mol azot gaz ve 20 mol hidrojen gaz yukardaki tepkimeyi verecek ekilde
kartrlyor. Belli artlar altnda yaplan ilem sonunda 5 mol amonyak gaz elde ediliyor. Bu
kimyasal denklemin tepkime konunu bulunuz?
zm:
=

ni n H 2 n N 2 n NH 3

i
H2
N2
NH 3
N 2 3H 2 2 NH 3

2.5 mol 7.5 mol

5 mol

Olarak tepkime gereklemektedir.Reaksiyona girmeyen azot ve hidrojen gazn bu tekime

reaksiyonunun dnda tutulur. Buna gre tepkime bu reaksiyon iin tepkime konu:
=

2.5 7.5 5

2.5mol
1
3
2

10.4.Tepkime i enerjisi
Sabit hacimde yryen kimyasal reaksiyonlar iin kullanlan bir kavramdr. Tanm
yle yaplabilir:
Sabit hacimde yryen bir kimyasal tepkimenin deien scakln ilk deerine
getirme srasnda ortaya kan s alveriine Tepkime enerjisi denir.
Bu demektir ki; sabit hacimde belli bir T0 scaklnda olan sistem, reaksiyon
baladktan sonra herhangi bir t annda scakl T deerine ular. Bu scaklk deiimi iin
sisteme verilen veya sistemden alnan s alverii Tepkime i enerjisi olarak da ifade edilir.
enerji, kimyasal olaylarn bulunduu sistemler iin genelde u faktrlere baldr:
-Scaklk
- Hacim
- Tepkime konu
Bu niceliklere bal olarak dnlen toplam i enerji, fonksiyonel olarak u ekilde
ifade edilir:
u=f(T, v; )
Bu fonksiyonun tam diferensiyeli alnrsa:
u

du

dT
v ,

T ,

dv

T ,v

Eitlik(10.4.1)

Eitlii ortaya kar. nc ksmi trev yani sabit scaklk ve sabit hacimde tm enerji
fonksiyonunun tepkime konu ile deime hz Tepkime i enerjisi olarak tanmlanr:
u

Eitlik (10.4.2)

T ,v

Bunun anlam nedir:

Bileenlerde sadece birisi dikkate alndnda 1 mol deime iin alnan veya verilen
enerji, molar olarak tepkime i enerjisini vermektedir.
U

p T
T

Eitlik (10.4.3)
v

Eitlik.10.4.3 Termodinamik eitlii hatrlanrsa,

Eitlik.10.4.1 aadaki ekilde formle edilebilir:
p
du nC v dT T

v ,

p dv ud

Eitlik (10.4.4)

Bu etlik bize neyi gsterir:

Bu eitlikten sabit scaklk ve sabit hacimde yryen tepkimeler iin toplam i enerji
ya da sistem ile ortam arasndaki toplam s alverii bulunur:

qv = u U d U *

Eitlik (10.4.5)

Bu eitliin anlam udur:

Bir kimyasal denklem hangi oranda deitirilirse tepkime i enerjisi de ayn oranda
deitirilir.Burada tepkime konunun somut olarak ne anlama geldii daha ak bir ekilde
ifade edilmektedir.
Bir kimyasal tepkime ters evrilerek yazlrsa tepkime i enerjisinin iareti de deiir.
enerji bir hal fonksiyonu olup du tam diferensiyeldir. Hacim ve tepkime konu
sabit iken tepkime i enerjisinin scaklkla deime hz:
U

v ,

(nC v )

C v

Eitlik (10.4.6)

T ,v

eklinde gsterilir:
C v : (Sabit hacimde tepkimeden kan maddelerin snma slar toplam) -

( Sabit hacimde tepkimeye giren maddelerin snma slar toplam)

Scaklk ve tepkime konu sabit iken enerjinin hacimle deime hz:
U

T ,

v ,

T ,v

v ,

T
T ,v

T
T ,v

v ,

T ,v

p
v ,

T ,v

eitlii bulunur:
p :

sabit scaklk ve sabit hacimde yryen bir kimyasal tepkimede

sistemdeki toplam basn deiimi

Not: Tepkime i enerjisi sabit hacimli kalorimetre ile llr.

rnek problem:
Scakl 200C de 1.25 g toluen sabit hacimdeki bir kalorimetrede tmyle yakldktan
sonra rnlerin scakl ilk scakla getirilirken sistemden ortama 40.0 kJ s akmaktadr.
Toluenin molar yanma i enerjisini hesaplaynz? Toluenin molar ktlesi= 92 g/mol
zm:
qv = 40.0 kJ
m=1.25 g
U ' qv/m (1 g toluenin yanmas sonunda kan s

1 mol toluenin yanmas sonunda kan s(=molar yanma ss)

U qv/m *92
U

40.0
* 92 2944kJ / mol
1.25

10.5.Tepkime Entalpisi
Sabit basn altnda gerekleen bir kimyasal tepkimede,deien scakl ilk deerine
getirebilmek iin gerekli olan s alveriine Tepkime entalpisi ( H )denir.
Standart koullar ( 1 atm, 250C ) altnda gerekleen bir kimyasal tepkimede deien
scakl standart koullardak scakla getirmek iin gerekli s alveriine Standart
tepkime entalpisi denir( H 0 ).
Tepkime entalpileri ekzotermik ve endotermik reaksiyonlae iin farkl iaretle gsterilir:
Entalpi deiimi (-) iaretli ise o tepkime darya s salmaktadr ve Ekzotermik
tepkime olarak isimlendirilmektedir.
Entalpi deiimi (+) olan bir tekime dardan s almaktadr. Bu trden tepkimeler
Endotermik tepkime olarak isimlendirilmektedir.
Entalpi hangi faktrlere baldr:
-scaklk
- basn
- tepkime konu (reaksiyon katsays olarak dnelim)
Bu faktrlere bal olarak fonksiyonel olarak ifade edilirse:
h=f(T,p, )
lgili faktrlere bal olarak tam diferensiyel alnrsa:
h

dh= T

p ,

dT
p

T ,

dp

d
T,p

Eitlik (10.5.1)

Bu eitlikte nc ksmi trevi tm entalpi fonksiyonunun tepkime konu ile deime hz

tepkime entalpisi olarak tanmlanr:
h

Eitlik (10.5.2)

T,p

Tepkime konunun sabit kalmas ne anlama gelmektedir:

Kimyasal tepkime ya balamamtr veya tamamlanmtr.
10.6. Oluum entalpisi
Bir kimyasal bileiin 1 molnn sabit basn ve elementlerinden oluumunu gsteren
tepkimenin entalpi deiimine o bileiin oluum entalpisi denir.
Standart koullarda elementlerden yola klarak yine standart koullarda 1 mol bileik
veren tepkimenin entalpisine Standart oluum entalpisi denir.
Gaz, sv ve kat haldeki tm elementlerin standart oluum entalpi deerleri
sfrdr:

H 0 =0

(gaz,sv,kat elementler)

Birok bileiin standart oluum entalpi deerleri deneysel yoldan bulunarak tablolarda
verilmitir.

H 0 =(Tepkimden kanlarn toplam standart oluum entalpileri)- (Tepkimeye

girenlerin toplam standart oluum entalpileri)
eitlii uyarnca Standart tepkime entalpisi kolaylkla bulunur.
Sabit scaklk ve basnta yryen tepkimeler srasndaki toplam s alverii:

qp = h Hd H

Eitlik (10.6.1)

Tepkime konuna bal olarak entalpinin katlar toplam s alveriini gsterir.

ayet kimyasal denklem ters yazlrsa tepkime entalpisinin de iareti deiir.
10.7. Tepkime entalpisinin scaklkla deiimi
H

(G TS )

V T
T

Termodinamik eitlii , Eitlik.10.5.1 de kullanlrsa:

v
dh nC p dT v T

dp Hd
p

Eitlik (10.7.1)

eitlii yazlabilir.
Basn ve tepkime konu sabit iken ,tepkime entalpisinin scaklkla deime hz:

p ,

(nC p )

C p

Eitlik (10.7.2)

T,p

C p (Tepkimeden kanlarn snma slar toplam) (Tepkimeye girenlerin snma

slar toplam)

Eitlik (10.7.3)

Tepkimeye giren ve kan element veya bileiklerin deneysel olarak bulunan ve

tablolarda gsterilen snma slar scakla bal olarak:
C p a bT cT 2 ..

Isnma slar scakla bal olarak verildii takdirde bilenlerin her biri iin bu eitlik
kullanlarak Eitlik 10.7.3 de yerine konulduktan sonra bulunan deer Eitlik 10.7.2 ye
tanr. Bu eitliin integrali alnrsa tepkime entalpisini scakla balayan eitlik bulunur:
H

C p
p ,

H C p T

Grld gibi farkl iki scaklk arasndaki deiim buradan hesaplanabilir.

10.8. Tepkime entalpisinin basnla deiimi
Scaklk ve tepkime konu sabit iken tepkime entalpisinin basnla deime hz:
H

T ,

= V

v T

p ,

T,p

T
T,p

V T

T,p

p ,

p ,

T,p

Eitlik(10.8.1)

p ,

V : molar hacim deiimi

Eitlik 10.8.1 de ki hacim deiimi ile hacim deiiminin scaklkla deiimi deneysel
H
p

olarak veya kuramsal hesaplanabilir. Bu nicelikler yerine konursa

deerinin

scakla bal eitlii bulunur. Bunun da integralinden iki basn arasndaki deiim
bulunabilir.
10.9. Tepkime entalpisi ve tepkime i enerjisi arasndaki iliki
u f (T , v, ) h pv
U H pV

Eitlik(10.9.1)

deal gaz karm gibi davranld kabul edilirse:

V v gaz RT / p

U H v gaz RT

Eitlik(10.9.2)

Neden bir tepkimede sadece gazlarn hacimlerindeki deime dikkate alnyor?

nk:
Tepkime srasnda sv ve kat fazlarn ortadan kalkmas veya ortaya kmasndan
kaynaklanan hacim deiimleri gazlardakine kyasla ok dk olduundan ,sv ve
katlardaki hacim deiimleri ihmal edilir.
ayet tepkimeye giren ve kan gazlarn mol saylar birbirine eit ise:

girenler

kanla

v gaz 0

ve bu durumda
U H

Eitlik(10.9.3)

nemli: Gazlarn yer almad tepkimelerin i enerjileri ile tepkime entalpileri birbirine
eittir.
alverii sabit hacimde yryen tepkimelerde sz konusu deildir.
al verii sabit basn altnda yryen tepkimelerde ortaya kmaktadr.
Yani;
w pV (H U ) v gaz RT

Eitlik(10.9.4)

Sabit bas ve sabit scaklkta hacim deiimi sfr ise i al verii de sfrdr.
Tepkime konunun maksimum 1 den farkl olacak ekilde yryen kimyasal
tepkimeler iin :

u U
h H
v gaz n gaz
w v gaz RT n gaz RT

Eitlik(10.9.5)

olup, tepkime i enerjisi ile tepkime entalpisi arasndaki iliki:

u h n gaz RT

Eitlik(10.9.6)

rnek problem:
ZnO(kat) + CO(gaz)

Zn(kat) + CO2(gaz)

tepkimesinin Standart tepkime entalpisini tablolardan yararlanarak bulunuz?

zm:

H 0 H 0 Zn( kat) H 0 CO2 ( gaz ) H 0 ZnO ( kat) H 0 CO( gaz )

H 0 0 ( 393.51) ( 348.28) ( 110 .53) 65.3kJ / mol

rnek problem:
C 6 H 14 ( sivi ) CH 4 ( gaz ) C 7 H 16 ( sivi ) H 2 ( gaz )

Tepkimesi veriliyor. Tepkimeye giren ve kan bileenlerin standart entalpileri:

H 0 (C 6 H 14 ) 4141.3kJ / mol
H 0 (CH 4 ) 882.0kJ / mol
H 0 (C 7 H 16 ) 4811.2kJ / mol
H 0 ( H 2 ) 286.1kJ / mol

verilmektedir. Standart tepkime entalpisini bulunuz?

H 0 tepk 'me (4811.2 286.1) (4141.3 882.0) 74.0kJ / mol

rnek problem:
Forml C8H18 olan sv 1 mol izo-oktan , sabit hacimde bir kalorimetrede
yakldktan sonra tepkime rnleri standart koullara getirilirken sistemden ortama 5800.0 kJ
s akmaktadr Buna gre:
a.) 250C deki tepkime i enerjisini
b.) Standart tepkime entalpisini
c.) Forml verilen maddenin standart oluum entalpisini hesaplaynz?
zm:
a.) Sabit hacimdeki bir tepkimede s alverii, i enerji deiimine eittir:
U 0 5800kJ / mol =qv

b.) Kimyasal tepkime denklemi yazlarak standart tepkime entalpisi tablolardaki

deerlerden alnarak hesaplanr.

C8H18(s)+ 25/2 O2(g)

8CO2(g) + 9H2O(s)

v gaz 8 12.5 4.5

H 0 5800000 ( 4.5) * 8.314 * 298 5811149 J / mol 5811.15kJ / mol

d.) Tablolardan yararlanarak izo-oktann standart oluum entalpisi hesaplanr:

H 0 tepkime 8 * H 0 (CO2 ) 9 * H 0 ( H 2 O) 25 / 2(O2 ) H 0 (C8 H 18 )

-5811.149=

8 * (393.51) 9 * (285.3) 25 / 2 * 0 H 0 izook tan

H 0 izook tan 95.3kJ / mol

10.10. Hess yasas
Bu yasaya gre:
Tepkime entalpileri bilinmeyen tepkimeyi bulmak iin tepkime entalpileri bilinen
tepkimeler arasnda toplama,karma,arpma,blme,ters evirme gibi ilemleri ile bilinmeyen
tepkime entalpisi hesaplanr.
rnek problem:
S(rhombic) + O2(g)

SO2(g)

S(monoclinic) + O2(g)

SO2(g)

H0tepkime= - 297.4 kJ/mol

H0tepkime= - 298.2 kJ/mol

Verildiine gre:

S(Rhombic)

S(Monoclinic)

H0tepkime=?

Yukardaki 2 eitlik dikkate alnarak nc tepkimenin tepkime entalpisi bulunabilir:

Nasl?
kinci eitlik birinci eitlikten karlrsa:
S(Rhombic) + O2(g)
SO2(g)
S(Rhombic)

SO2(g)

H0tepkime= - 297.4 kJ/mol

S(Monoclinic)+O2(g) H0tepkime=298.2 kJ/mol

S(Monoclinic)

H0tepkime= 0.8 kJ/mol

10.11. Fiziksel olaylar srasndaki Entalpi Deiimleri

Kristal dnm, erime,buharlama , sblimleme , znme fiziksel olaylardr. Bu
ilemler srasnda entalpi deiimleri ortaya kar. Baz maddeler iin bu tr fiziksel olaylar
oluumundaki entalpi deiim deerleri tablolarda verilmitir.
10.12. Erime ve Buharlama entalpisi
rnein: 1 mol buzun 00C de ve 1 atm basn altnda faz deiimi ile sv faza gemesi iin
erime entalpisi:
H2O(k)

H2O(s)

H0erime =6.01 kJ/mol

rnein: 1 mol suyun 1 atm. basn altnda ve 1000C de faz deiimi ile kaynayarak buhar
fazna gemesi iin buharlama entalpisi:
H2O(s)

H2O(b)

H0kaynama =40.66 kJ/mol

Donma entalpisi erime entalpisine ters iaretle eittir (H0donmaa = -6.01 kJ/mol)
Younlama entalpisi, buharlama entalpisine ters iaretle eittir ( H0younlama = 40.66 kJ/mol)
rnek soru: Suyun sblmleme entalpisi nasl bulunur?
Erime ve buharlama entalpilerinin toplam sblimleme entalpisini verir:
H0sblimleme= H0erime + H0kaynama = 6.01+40.66=46.67 kJ/mol
10.13.znme entalpisi
Standart koullarda 1 mol maddenin belli miktardaki bir zcde znmesi
srasndaki s al veriine Standart znme entalpisi denir.
Elektrolit zeltilerin hazrlanmasnda iyonik etkilemeleri ihmal etmek iin sonsuz
miktar zc alnr:
rnek: 1 mol HCl gaznn sonsuz miktarda suda znmesi iin standart znme
entalpisi:
HCl (g)

HCl (aq)

H0znme = -75.14 kJ/mol

aq : suda znm hali

Baz maddelerin standart znme entalpileri tablolarda verilmitir.
10.14. Kimyasal olaylar srasndaki Entalpi Deiimleri
Oluum entalpisi, Yanma entalpisi, Ba oluum entalpisi, Ba bozunum entalpisi,
Hidratlama entalpisi, Hidrojenlenme entalpisi, yonlama entalpisi, Atomlama entalpisi,
Kristal entalpisi ile kimyasal olaylar srasndaki s al verii aklanmaktadr.
10.15.Oluum entalpisi

1 mol bileiin elementlerinden oluumunu veren tepkimelerin sabit basn ve

scaklktaki entalpisine Oluum entalpisi denir. Standart koullardaki entalpilerine standart
oluum entalpisi denir.
rnekler:
Suyun oluum entalpisi:
H2(g) + 1/2O2(g)

H2O (s)

H0(H2O,s)= -285.85 kJ/mol

H2O (g)

H0(H2O,g)= -241.84 kJ/mol

CO2

H0(CO2 ,g)= - 359.51 kJ/mol

Su buharnn oluum entalpisi:

H2(g) + 1/2O2(g)
Karbondioksitin oluum entalpisi
C(grafit) + 1/2O2(g)

Birok organik be inorganik maddelerin Standart oluum entalpileri tablolarda

verilmitir.
10.16.Yanma entalpisi
Kat, sv ve gaz halindeki maddelerin oksijen ile vermi olduklar tepkime sonundaki
s al verilerine yanma entalpisi denir. Standart koullardaki maddeler yakldktan sonra
oluan rnlerin yeniden standart koullara getirilmesi srasndaki s alveriine standart
yanma entalpisi denir.
rnek: propan gaznn yanma tepkimesi ve standart yanma entalpisi
C3H8 (g) +

5 O2

3 CO2 +

4H2O

H0= -2220 kJ/mol

Yanma olay srasnda sistemden ortama s aktndan dolay yanma entalpisi daima
eksi iaretlidir.
Birok organik maddenin standart yanma entalpileri tablolarda verilmitir.
10.17. Is deerleri
Standart koullardaki hacmi 1 m3 olan bir gaz sabit basn altnda yakldnda aa
kan sya o yaktn s deeri denir.
Yanma sonunda su sv hale gelmi iseaa kan sya o yaktn st s deeri denir
Yanma sonunda su buhar haline gelmi ise aa kan sya o yaktn alt s deeri
denir.
10.18. Ba bozunum ve ba oluum entalpisi:
Sabit basn ve sabit scaklkta 1 mol ban bozunmas iin gerekli sya ba enerjisi
veya ba bozunum entalpisi denir
Ayn artlarda 1 mol ban olumas srasnda aa kan sya ba oluum entalpisi
denir.

Ba bozunum entalpisi mutlak deerce ba oluum entalpisine eittir. Ba bozunum

entalpisi art iaretli olduu halde ba oluum entalpisi eksi iaretlidir.
Ayn atomlar arsnda bulunan 2 yada 3 ban bozunum entalpileri birbirinden
farkldr.rnek: C-N, C==N , rneklerinde , karbon ve azot arasndaki ba enerjileri
birbirlerinden farkldr. Atomlar 1, 2 veya 3 ba ile birbirlerine balanmaktadrlar.Baz
molekllerdeki balar iin Standart ba bozunum entalpi deerleri tablolarla verilmitir.
rnekler: O-H arasndaki ban bozunumu farkl molekllerde farkldr:
Sudaki O-H bann standart bozunma entalpisi : H0= 499 kJ/mol
Hidroksil grubundaki O-H bann standart bozunma entalpisi H0= 428 kJ/mol
Metil alkol grubundaki O-H bann standart bozunma entalpisi H0= 437 kJ/mol
olarak llmtr.
Standart ba bozunum entalpileri kullanlarak kimyasal tepkimelerin standart
tepkime entalpileri bulunur.:
Tekime entalpisi= (Tepkimeye girenlerin balarnn standart tepkime entalpileri
toplam)- (Tepkimeden kanlarn balarnn standart tepkime entalpileri toplam)
10.19. Atomlama entalpisi
1 mol element veya bileik iindeki tm atomlarn birbirinden ayrlmas srasndaki
standart entalpi deiimine standart atomlama entalpisi denir .
rnek:
Na(k)

Na(g)

H0a =107 kJ/mol

Ayn zamanda standart sblimleme entalpisi olarak da ifade edilebilir:

Baz elementlerin standart sblimlememe entalpileri tablolarda verilmitir.
10.20. yonlama Entalpisi
Sabit basn ve sabit scaklkta gaz halindeki 1 mol element veya bileikten 1 mol
katyon veya anyon olumas srasndaki s al veriine yonlama entalpisi denir:
X(g)

X+(g) + e-(g)

H0iyonlama =

Standart iyonlama entalpisi ile standart iyonlama i enerjisi arasndaki iliki:

H0iyonlama = Uiyonlama + nRT
n= (1 mol X+(g) + 1 mol e-(g))- 1 mol X(g)=1
Standart iyonlama i enerjisine yonlama enerjisi ( Ei ) denir.
H0iyonlama=Ei + RT
Oluan katyon ikinci defa iyonlaabilir:

Eitlik(10.20.1)

X+(g)

X+2(g) + e-(g)

Ei,2 =

Bu iyonlama srasndaki i enerji deiimine ikinci iyonlama enerjisi (Ei,2 ) denir

Baz elementlerin birinci ve ikinci iyonlama enerjileri tablolarda verilmitir.
10.21. Elektron alma entalpisi (H0el.alma)
Standart artlarda gaz fazndaki atom veya molekllerin elekton almasyla oluan s
al veriine Standart elektron alma entalpisi denir. Eitlik 10.20.1 de RT deeri ihmal
edilebilir. Bu durumda entalpi i enerjisine eit olarak kabul edilebilir. Standart elektron alma
entalpisinin tersine Elektron affinite ( Eelek.aff.) denir.
Standart elektron kazanma entalpisi ile elektron affinitesi arasndaki bant:
H0elek.alma=Uelek.alma RT= - Eelek.aff. RT
Elektron affiniteleri art iaretli ve byk olanlarn elektron alma yatknlklar ok
byk, eksi iaretli ve kk olanlarn ise elekton alma yatknlklar ok kktr.
Baz elementleri Elektron affinite deerleri:
Element

Eelek.aff (kJ/mol)

72.8

Li

59.8

-7.0

322.0

Ne

-29.0

He

-21.0

10.22. Hidratlama entalpisi

Gaz halindeki iyonlarn sulu zeltide hidratlamas srasndaki standart entalpi
deiimine Standart hidratlama entalpisi (H0Hidratlama) denir.
rnek:
Na+(g) + Cl-(g)

Na+(aq) + Cl-(aq) (NaCl(aq)) H0Hidratlama =-783.4 kJ/mol

Baz bileikler iin standart hidratlama entalpileri tablolarda verilmitiri

Gaz halindeki iyonlarn su yerine baka zcler ierisinde znmesi srasndaki
entalpi deiimine standart solvatasyon entalpisi( H0sovatasyon ) denir.
rnek:
Hidrojen gaznn sulu zeltideki hidrojen iyonuna dnm srasndaki standart
tepkime entalpisi tm scaklklar iin sfr kabul edilir:
H2 (g)

H+(aq)

( H0, H+, aq)=0

yonik bileiklerin zeltideki oluum entalpileri , bileiklerde bulunan

iyonlarn zeltideki oluum entalpileri toplamna eittir.

Bileiklerin sulu zeltide oluum entalpilerinden yararlanarak dier

iyonlarn zeltideki oluum entalpilerine geilir. Baz iyonlar iin bu
deerler tablolarda verilmitir.

rnek soru: HCl in sulu zeltisinde oluum entalpisi -167 kJ/mol dr. NaCl n
sulu zeltideki oluum entalpisi - 407 kJ/mol olarak veriliyor.
a.) Cl- iyonunun sudaki oluum entalpisi nedir?
b.) Na+ iyonunun sulu zeltideki oluum entalpisi nedir?
zm:
a.)
H+(aq) + Cl-(aq)

HCl(aq)

H0oluum ( HCl)aq))= H0oluum (H+(aq)) + H0oluum (Cl- (aq))

-167 = 0 + H0oluum (Cl- (aq))
H0oluum (Cl- (aq)) = - 167 kJ/mol
b.)
Na+(aq) +Cl-(aq)

NaCl (aq)

H0oluum ( NaCl)aq))= H0oluum (Na+(aq)) + H0oluum (Cl- (aq))

-407 = H0oluum (Na+(aq)) + (- 167)
H0oluum (Na+(aq)) = - 407 + 167 = - 240 kJ/mol
Not: Hidrojen elementinin (gazn) sulu zeltide hidrojen iyonuna dnm iin
standart tepkime entalpisi her scaklkta sfr olduu halde;
Gaz halindeki Hidrojen iyonunun sulu zeltide hidrojen iyonuna dnm
(=hidrojen iyonunun hidratlamas):
H+(g)

H+(aq)

H0Hidratlama (H+ ,aq)= - 1090 kJ/mol

10.23. Kristal entalpisi

Bir katnn gaz halindeki iyonlara ayrlmas srasndaki entalpi deiimine
Standart kristal entalpisi (=kristal enerjisi) denir.
rnek:
NaCl(k)

Na+(g) + Cl- (g)

H0kristal = 787 kJ/mol

Baz kat bileikler iin Standart kristal entalpi deerleri tablolarda verilmitir.

rnek soru: Standart ba bozunum entalpilerinden(ba enerjisi) yararlanarak

propan iin standart oluum entalpisini bulunuz?
zm:
3C(grafit) + 4 H-H

Denklemde grld gibi grafit halinde 3C atomlar, ve 4 Hidrojen ba

bozunur. Bunun yerine 2 C-C ba ve 8 C-H ba oluur. Standart oluum entalpisi molar
cinsinden verildiine gre:
3 mol C(grafit) ve 4 mol H-H ba bozunur
2 mol C-C ba ve 8 mol C-H ba oluur
Tablolardan yararlanarak propan iin standart oluum entalpisi bulunur:
H0oluum ( C3H8 ,g) ={3H0(C,graphite)+4H0(H-H}- [ 2H0(C-C)+8H0(C-H)]
H0oluum ( C3H8 ,g)= [3*(716.7) + 4(436) ]- [2*348+ 8*(412)= -97.9 kJ/mol

10.25 Kimyasal Denge

Kimyasal denge, iki ynl bir reaksiyonda; rnlerin meydana geli hznn,
rnlerden tekrar reaksiyona girenlerin meydana geli hzna eit olduu hal olarak
tanmlanabilir.
Reaktantlar

rnler

Kimyasal denge kurulduktan sonra koullar deitirilmedike (scaklk ve basn sabit

tutulduunda, ortama herhangi bir madde ilave edilmediinde) maddelerin (rn
ve reaktantlarn) deriimlerinde ileri ve geri yne olan reaksiyonlar eit hzda yryp

gittiinden zamana bal olarak bir deime olmaz. Dinamik bir denge kurulmu olur.
Kimyasal olaylarda madde akmnn yrtc kuvveti kimyasal potansiyel farkdr.
Maddeler, kimyasal potansiyellerin byk olduu yerden kk olduu yere kayar. Kimyasal
potansiyeller eit olduunda denge kurulmu olmaktadr.
Tepkime sresince, tepkimeye giren ve kan maddelerin kimyasal potansiyelleri
,tepkime konuna bal olarak deiecektir. Bu deimeler, kimyasal potansiyel farkn
azaltacak ynde olur. Kimyasal potansiyel fark sfr olduunda Tepkime serbest entalpisi de
sfr olacaktr.Yani; iki yne dore net madde akm duracaktr. Bu durumda tepkimeye giren
ve tepkimeden kan bileenlerin mol miktarlarnn sabit kald anda Kimyasal denge ye
ulalm olmaktadr:
g

G
T,p

Denge konumuna gelindiinde tepkime konu da sabit bir deere ulamaktadr.

Denge sabiti Kd 'nin bykl o reaksiyonun dengeye varmadan nce ne kadar
ilerleyebileceinin bir lsdr. Yksek bir Kd deeri, dengede rnlerin yksek,
reaktantlarn dk deriimde bulunmas anlamna gelir. Aksine, dk bir Kd deeri ise,
dengedeki reaktant deriiminin rnlerinkine kyasla fazla olmas demektir
10.26 Chtelier kural
Dengedeki bir sisteme dardan herhangi bir etki yapldnda, sistem bu etkiyi
azaltacak yne kendiliinden kayar ve denge yeniden kurulur
Kimyasal dengeyi etkileyip deimeye zorlayabilecek bu d etkiler
neler olabilir?
-Bir Reaktantn Veya rnn lavesi ya da Uzaklatrlmas (Deriim Etkisi
-Gaz Faz Denge Reaksiyonlarnda Hacim (Veya Basn) Deiiklii
- Scaklktaki Deime
- Katalizrler ve Denge
10.27. deal Gaz karmlarnda Homojen Kimyasal Denge
Tipik bir homojen gaz tepkimesi:
A A( gaz ) B B ( gaz ) ... C C ( gaz ) D D ( gaz ) ...

eklinde yazlr. Denge durumunda her iki tarafn kimyasal potansiyelleri birbirine eittir:
G C C D D ... ( A A B B ...)

Bir bileenin kimyasal potansiyeli:

i i RT ln ppi0

p
p
p
p
0
0
G ... C C RT ln C0 D D RT ln D0 ... A A0 RT ln A0 B B0 RT ln B0
p
p
p
p

G ... C

0
D

...

B
0
A

0
B

( pC / p 0 ) C ( p D / p 0 ) D
RT ln
( p A / p 0 ) A ( p B / p 0 ) B

G G 0 RT ln Q p

Qp = Tepkime oran
Denge durumunda Qp=Kp ve
G 0 RT ln K p

Denge sabitleri ksmi basnlara gre yazld gibi molarite ve mol kesirlerine bal olarak da
yazlabilir:
Kp

Ksmi basnca gre bulunan denge sabiti

Kc

Molariteye gre bulunan denge sabiti

Kx

Mol kesire gre bulunan denge sabiti

Aralarndaki bant:
RTc 0
0
p

K p K c

Kp=Kx(p/p0)
=0 ise
Kp=Kx=Kc
10.28. Denge sabitinin scakla ball
ln K p

G 0
H 0 S 0

RT
RT
R

d ln K p / dT

H 0
RT 2

vant Hoff denklemi

:
H 0
d ln K x / dT
RT 2
Kp

ile K x in scakla ball ayndr.

K p ile K c yi birbirine balayan bantdan:

ln K p ln K c ln R ln T

Scakla bal trevden:

d ln K p / dT d ln K c / dT / T

H 0
d ln K c / dT / T
RT 2

d ln K c / dT

U
RT 2

ntegral alnarak ln K c scakla balanr.

rnek problem:
N2O4(g)

2NO2(g)

Tepkimesi iin standart koullarda

Kp , Kc, Kx denge sabitlerini bulunuz?
zm:
Tablolardan yararlanarak standart oluum serbest entalpilerden
G 0 2G 0 ( NO2 , g ) G 0 ( N 2 O4 , g )
G 0 2 * 51.31 97.89 4.73kJ / mol
ln K p

G 0
4730

1.91
RT
8.314 * 298

RTc 0
0
p

K c K p

K x K p
0
p

0.082 * 298
0.148

K p 0.148
1

6.05 * 10 3

1.148 *10 1 0.148

10.30. Heterojen Kimyasal Denge

ok fazl tepkime dengelerine Heterojen Kimyasal denge denir.
A A(kat) B B ( gaz ) ... C C ( sv) D D ( gaz ) ...

Bu heterojen sistemde B ve D bileenleri gaz halinde, A bileeni kat, C bileeni sv

fazdadr.
Dengede kimyasal potansiyeller eitliinden

p
G ... C C0 D ( D0 RT ln 0D ) A A0 B ( B0 RT ln B0 ..
p
p

G (... C D ) ( A B ..) RT ln
0
C

0
D

0
A

0
B

..( p Z A / p 0 )

( p B / p 0 ) B

G G 0 RT ln Q p

Eitlik(10.30.1)

G 0 RT ln K p
G RT ln(Q p / K p )

Grld ekilde kat ve sv fazlar denge sabitinde yer almamaktadr.

K K K p

Eitlik(10.30.2)

10.31. Tepkime Entropisi

Sabit basn ve sabit scaklkta tepkime kon7unun maksimum deeri 1 mol
olacak ekilde yani birim olarak seilen bir stokiyometrik denkleme gre yryen kimyasal
tepkimeler srasnda sistemdeki entropi deiimine Tepkime entropisi denir.
u bilgileri hatrlayalm:
- Kimyasal olaylarda sistemin dzensizlii , yani entropisi deimektedir.
- Sistemi daha dzenli hale getiren olaylar entropiyi drr.
- Entropi artan scaklkla artar.
-Erime ve buharlama gibi olaylarda sistemin entropisi artar
- Younlama ve donma gibi olaylarda entropi azalr.
Bir kimyasal tepkimenin yrd kapal bir sistemin tm entropi fonksiyonu
scaklk, basn, ve tepkime konuna bal olarak:
s=f(T,p, )
Tam diferensiyeli alnrsa:
s

ds= T

dT
p
p ,

T ,

dp

Eitlik(10.31.1)

T,p

Buradaki sabit scaklk ve basntaki nc ksmi trevi Tepkime entropisi olarak

tanmlanr:
s

Eitlik(10.31.2)

T,p

yle ki;
Tepkime konu 1 mol deitiinde tm entropideki deime tepkime entropisini verir.

s S d S *

Eitlik(10.31.3)

Bir kimyasal tepkimenin yrd kapal bir sistemin tm entropi fonksiyonu

scaklk, hacim, ve tepkime konuna bal olarak:
s=f(T,v, )
Tam diferensiyeli alnrsa:
s

ds= T

dT
v ,

T ,

dv

d
T ,v

S v

T,p

v indisi sabit hacimde yryen sistemler iin kullanlyor.

Standart koullardaki maddelerden klp bir kimyasal tepkime ile yine standart
koullardaki yeni maddelere geilmesi srasndaki entropi deiimine Standart tepkime
entalpisi denir.
s

S 0
1atm , 25C 0

S 0 (Tepkime rnlerinin molar entropileri)- (Tepkimeye girenlerin molar entropileri)

Tersinir kimyasal olaylar srasnda evrenin entropisi deimez. Tersinmez kimyasal

olaylarda evrenin entropisi artar.
Sabit basn ve scaklkta yryen kimyasal olaylar srasnda evrendeki entropi
deiimi:
S evren S

H
T

Eitlik(10.31.4)

S : Tepkime entropisi
H : Tepkime entropisi

Buna gre evrenin entropisinin pozitif ve mutlak deerce yksek olmasna neden olan
btn faktrler kimyasal olaylarn kendiliinden olmasn kolaylatrr.
Evrenin entropisini eksi yapan kimyasal olaylar kendiliinden yrmez..Dardan
mdahaleye ihtiya vardr.
Evrenin entropisi sfr olduu durumda da kimyasal olaylar kendiliinden olmaz.
Tersinir olarak yrtlmesi gerekir. Olaylarn tersinir olarak yryebilmesi iin ok kk
mdahalelerle denge durumu geriye dnebilecek ekilde tasarlanmaldr.
10.32. Tepkime entropisinim scaklkla deiimi

p ,

(nC p / T )

C p / T

Eitlik(10.32.1)

T,p

Bu eitlie gre tablolardan snma slar bulunup scakla blndkten sonra yine scakla
bal integrali alnarak tepkime entropisini scakla balayan eitlik bulunur.
10.33. Tepkime entropisinin basnla deiimi
S

T ,

p ,

T,p

T,p

p ,

p ,

Eitlik(10.33.1)

V : Tepkime srasndaki hacim deiimi

Bu hacim deiiminin scaklkla deime hz kuramsal veya deneysel olarak bulunarak

integral alnp, tepkime entropisini basnca balayan eitlie geilir.
rnek problem: Termodinamik tablolardan yararlanarak :
K(k) + NaCl(k)

Na(k) + KCl(k)

Tepkimesinin :
a.) Standart tepkime entalpisini
b.) Standart tepkime entropisini
c.) Tersinir yrtlen tepkime srasndaki s alveriini
d.) Ortamdaki entropi deiimini
e.) Evrendeki entropi deiimini

bulunuz?

zm:
a. )

H 0 Tepkime H 0 ( Na, k ) H 0 ( KCl , k ) H 0 ( K , k ) H 0 ( NaCl , k )

H 0 Tepkime 0 (436.75) 0 (411.15) 25.60kJ / mol
b.)

S 0 Tepkime S 0 ( Na, k ) S 0 ( KCl ), k S 0 ( K , k ) S 0 ( NaCl , k )

S 0 Tepkime 51.21 82.59 64.18 72.13 2.51J / Kmol
c.)
qTers=T S 0 =298*(-2.51)=-747.98J/mol
d.)
S 0 Ortam

e.)

qortam/T= - H 0 / T 25600 / 298 85.91J / Kmol

(ekzotermik)

S 0 evren S 0 ortam S 0 sistem 85.91 2.51 83.4 J / Kmol

Bu deerlendirmelere gre bu reaksiyon kendiliinden olur.
10.34 Tepkime Serbest i Enerjisi(= Helmholtz enerjisi)
Serbest i enerji fonksiyonu, scaklk,hacim ve tepkime konuna bal olarak:
a=f(T,v, ) eklinde gsterilir.
Tam diferensiyeli alnrsa;
a

da

dT
v ,

T ,

dv

d
T ,v

da sdT pdv Ad
a

Tepkime serbest i enerjisi

T ,v

A 0 : Standart tepkime i enerjisi

Kimyasal olaylardaki serbest i enerji deiimi, sabit hacim ve scaklkta tersinir
olarak yrtlen kimyasal tepkimelerdeki ie eittir. Sz konusu i elektriksel i olabilir.
Evrendeki entropi deiimi,tepkime serbest i enerjisi,tepkime i enerjisi, tepkime
entropisi arasndaki bant::
-T S evren A U TS

(v sabit)

Bu eitlie gre; evrenin entropisini arttran kjimyasal tepkimeler kendiliinden

(=tersinmez) yrmekte olup,tepkime i enerjisi eksi iaretli olan tepkimeler kendiliinden
olur.
Tam diferensiyel olma koulundan hacim ve tepkime konu sabit iken tepkime serbest
i enerjisinin scaklkla deime hz:
A

v ,

S
T ,v

A U TS
(A / T )

v ,

U
T2

Gibbs-Helmholtz denklemi

Eitlik(10.34.1)

Bu denklem ile tepkime serbest i enerjisi ile tepkime i enerjisi birbirine balanm olur.
Tam diferensiyel olma koulundan tepkime i enerjisinin hacimle deime hz:
A

T ,

p
T ,v

bilindiinde integral alnarak A bulunur.

10.35. Tepkime Serbest Entalpisi(=Gibbs enerjisi)

Serbest entalpi fonksiyonu, scaklk,basn ve tepkime konuna bal olarak yazlrsa:
g=f(T,p, )
bunun da tam diferensiyeli alnrsa:
g

dg= T

dT
p
p ,

T ,

dp

d
T,p

dg sdT vdp Gd
g

Tepkime serbest entalpisi

T,p

g
G 0

1bar , 25 0 C

Standart tepkime serbest entalpisi

Bir bileiin elementlerinden oluumunu gsteren kimyasal tepkimelerin standart

koullardaki serbest entalpi deiimine standart oluum serbest entalpisi denir. Elementlerin
standart oluum entalpileri sfr kabul edilerek bileiklerin standart oluum entalpileri
tablolardan faydalanlarak bulunur.
Kimyasal olaylardaki serbest entalpi deiimi, sabit basn ve sabit scaklkta tersinir
olarak yrtlen kimyasal tepkimeler srasndaki ie eittir. Not: Bir kap iinde her durumda
tersinmez olarak yryen tepkimeler ancak bir pil iinde tersinir olarak yrr.
Pillerden alnan maksimum elektriksel i:
we = -nFE
E=Elektromotor kuvveti
F=96500 C/mol
n= tepkimde molar elektron says
Standart koullarda alan bir pil iin:
-we ,maksimum= - G 0 nFE 0 (tersinir yryen tepkimeler)
E0 = standart elektromotor kuvveti
10.36. Kendiliinden olan Kimyasal olaylar
Kendiliinden yryen olaylar srasnda evrendeki entropi deiimi art iaretlidir.
Tepkime serbest entalpisi eksi iaretli olan kimyasal olaylar kendiliinden(=tersinmez)
yrr.

Evrendeki entropi deiimi ve ayn zamanda tepkime serbest entalpisi sfr olan
kimyasal olaylar denge konumunda olduundan, ancak dardan yaplan kk etkiler ile
tersinir olarak yrtlebilmektedirler.
10.37. Tepkime serbest entalpisinin scaklkla deiimi
Tam diferensiyel olma koulundan basn ve tepkime konu sabit iken tepkime serbest
entalpisinin scaklkla deime hz:
G

p ,

T,p

Ve
G H T S

Bu eitliklerden yola klarak tepkime serbest entalpisini tepkime entropisine balayan

eitlik:
( G / T )

p ,

H
T2

Gibbs-Helmholtz denklemi

Eitlik(10.37.1)

10.38. Tepkime serbest entalpisinin basnla deiimi

Tam diferensiyel olma koulundan scaklk ve tepkime konu sabit iken tepkime serbest
entalpisinin basnla deime hz:
G

T ,

V
T,p

rnek problem: Hidrojen Bromrn elementlerinden oluumu reaksiyonu:

1/2H2 + 1/2Br2

HBr

Tablolardan yararlanarak, 1 atm ve 800 K deki

a.) Tepkime entalpisini
b.) Tepkime entropisini
c.) Tersinir yoldan yrtlen tepkime iin s alveriini
d.) Ortamdaki entropi deiimini
e.) Evrendeki entropi deiimini
800

Veriler: S

800

S
0

(C

/ T ) * dT

298

800

H 800 H 0 olu ;um

298

dT

hesaplaynz?

zm:

H 0 olu ;um 36400 J / mol

800

H 800 H 0 olu ;um

dT

298

H 800 36400 C p (800 298)

C p ( HBr ) C p (urunlertoplami ) C p ( girenlerto plami )
C p 29.142 (1 / 2 * 36.020 1 / 2 * 28.824) 3.280 J/K.mol

H 800 36400 3.280(800 298) - 3.805* 104 kJ/mol

b.)
S 0 S 0 (urunlertoplami ) S 0 ( girenlerto plami )
S 0 198.70 (1 / 2 * 245.46 1 / 2 * 130.684) 10.63 J/K mol
800

S 800 S 0

(C

/ T ) * dT

298

800

dT
T
298

= 10.63 ( 3.280)
=10.63- 3.280 * ln

800
298

= + 7.39 J/K mol

c.)
qtersinir=T S 800 =800*(+7.39)= +5912 J/mol
d.)

S 800 ort . H 800 / T qort/T= +38050*/800= + 47.55 J/K mol

e.)
S 800

evren

S 800 sistem S 800 ort 7.39 47.55 54.94 J / Kmol

Bu sonulara gre 800 K de HBr kendiliinden oluur.

Not: Isnma ss scakln fonksiyonu olarak verilirse bu durumda farkl yol takip
edilir. Burada snma ss scaklktan bamsz olarak , her scaklkta sabit olarak
kabul edildi