senior five chemistry continued......(mr.

obonyo)

Deviations from ideal behavior (non-ideal behaviour of gases)

Gases tend to have ideal behaviour at conditions of;

 High temperature; because the gas molecules

will have enough kinetic energy to overcome
intermolecular forces of attraction.
 Low pressure: because the gas molecules will
be far apart and hence negligible
intermolecular forces of attraction.

However, in reality, no gas totally obeys the gas

laws. This is because more precise measurements
revealed that gas molecules have substantial
volumes and the molecules have attractive or
repulsive forces between them.

Gases that do not obey all the gas laws are called
real gases.

Real gases depart from ideal behaviour at high pressures and low temperatures.

The deviations from ideal behaviour by gases can be shown by plotting a graph of PV against P for
different gases at a constant temperature.

For an ideal(perfect) gas, at a given temperature, a straight horizontal line is obtained when PV is
plotted against P. This is because for such a gas, Z=1. But no such gas exists thus the concept is a
theoretical one.
𝑃𝑉
As pressure tends to zero, the factor 𝑅𝑇 (compressibility factor Z) of a gas tends to one, i.e. it tends
towards that of an ideal gas. By definition, compressibility factor is a measure of deviation from
ideal gas behaviour.

As pressure increases from zero, there is a slight fall in the value of Z (i.e. there is deviation from
ideal behaviour). This is because there are molecular attractions between the gas molecules and
this makes the volume occupied by a gas even much smaller.

At high pressures, gas molecules are very close to one another and thus, stronger molecular
attractions exist between them. This reduces the volume occupied by the gas molecules. Also, gas
molecules do not strike the walls of the container with full impact. This is because there are
dragged back by other molecules due to molecular attractive forces. This makes the pressure
exerted on the walls of the container to be low.

At very high pressures, the forces between the gas molecules are repulsive forces, and the value of Z
starts to rise. This is because the repulsive forces increase the volume occupied by the gas
𝑃𝑉
molecules and thus, the factor 𝑅𝑇 becomes greater than one and hence the rise.

Hydrogen does not show negative deviation from the ideal behaviour because; hydrogen molecules
are smaller with very low molecular mass. This makes the forces of attraction between the
molecules so weak. Also, the hydrogen molecules are non-polar and this further makes the
intermolecular forces weaker.

1|Page
For carbon dioxide, the curve falls much more (deviates more) than that of hydrogen and nitrogen.
This is because carbon dioxide molecules have high molecular mass and are bigger in size and this
makes the intermolecular forces much stronger. Hence, greater deviation from ideality. Carbon
dioxide gas can therefore, be easily liquefied than nitrogen and hydrogen.

Dalton’s law of partial pressure;

This law is concerned with pressures exerted by the constituents in a mixture of gases that do not
react chemically with each other.
John Dalton, an English scientist (in 1801), established the relation between the pressure of the
mixture of gases and individual pressures of the constituent gases.
This relationship is known as Dalton's law of partial pressures and states that:
“The total pressure exerted by a mixture of non-reactive gases is equal to the sum of the individual
partial pressures of gases at a given temperature”.
Partial pressure of a gas is the pressure that each gas would exert if it alone occupied the volume of
the mixture of the gases of which it was a component at the same conditions.

Thus, for a mixture of gases A, B, C and D; we can write 𝑃𝑇𝑜𝑡𝑎𝑙 = 𝑝𝐴 + 𝑝𝐵 + 𝑝𝐶 + 𝑝𝐷 .

Where 𝑝𝐴 , 𝑝𝐵 , 𝑝𝐶 𝑎𝑛𝑑 𝑝𝐷 are partial pressures of each gas and 𝑃𝑇𝑜𝑡𝑎𝑙 is the total pressure.

If the individual gases behave ideally, it implies that the mixture of gases also behave ideally and
must conform to the ideal gas equation; 𝑃𝑉 = 𝑛𝑅𝑇.

Consider two gases A and B; 𝑃𝑇𝑜𝑡𝑎𝑙 = 𝑝𝐴 + 𝑝𝐵

If the gases are ideal, then 𝑃𝑇𝑜𝑡𝑎𝑙 𝑉 = 𝑛 𝑇𝑜𝑡𝑎𝑙 𝑅𝑇 … … … … … … … … . … (𝑖)

⇒ 𝑝𝐴 𝑉 = 𝑛𝐴 𝑅𝑇 … … … … … . … … … … . … … … . (𝑖𝑖)

𝑝𝐵 𝑉 = 𝑛𝐵 𝑅𝑇 … … … … … … … … … … … … … . (𝑖𝑖𝑖)
𝑃𝐴 𝑉 𝑛𝐴 𝑅𝑇 𝑃𝐴 𝑛𝐴
Dividing expression (𝑖𝑖) by (𝑖) gives: 𝑃𝑇𝑜𝑡𝑎𝑙 𝑉
=𝑛 ⟹𝑃 =𝑛
𝑇𝑜𝑡𝑎𝑙 𝑅𝑇 𝑇𝑜𝑡𝑎𝑙 𝑇𝑜𝑡𝑎𝑙

𝑛𝐴
Therefore, we can write 𝑝𝐴 = × 𝑃𝑇𝑜𝑡𝑎𝑙 which is the expression for partial pressure of
𝑛𝑇𝑜𝑡𝑎𝑙
component A.
𝑛𝐵
Similarly, the expression for partial pressure of component B is 𝑝𝐵 = 𝑛 × 𝑃𝑇𝑜𝑡𝑎𝑙
𝑇𝑜𝑡𝑎𝑙

Recall; 𝑛 𝑇𝑜𝑡𝑎𝑙 = 𝑛𝐴 + 𝑛𝐵
𝑛𝐴 𝑛𝐵
Thus, the expressions and are called the mole fraction of A and B respectively. We can
𝑛𝑇𝑜𝑡𝑎𝑙 𝑛𝑇𝑜𝑡𝑎𝑙
also write:
𝑛𝐴 𝑛𝐵
(i) Mole fractions of components A and B as 𝑋𝐴 = and 𝑋𝐵 = respectively.
𝑛𝑇𝑜𝑡𝑎𝑙 𝑛𝑇𝑜𝑡𝑎𝑙
(ii) Partial pressures of components A and B as 𝑝𝐴 = 𝑋𝐴 × 𝑃𝑇𝑜𝑡𝑎𝑙 and 𝑝𝐵 = 𝑋𝐵 × 𝑃𝑇𝑜𝑡𝑎𝑙 respectively.
(iii) For an ideal mixture, 𝑋𝐴 + 𝑋𝐵 = 1

Note:

 The mole fraction of a given component is the ratio of number of moles of that component
to the total number of moles of all the components in a mixture.

2|Page
  The term mole percentage may be used instead of mole fraction. Mole percentage is simply
mole fraction expressed as a percentage.

Examples:

1. A mixture of 0.6 moles of nitrogen, 0.8 moles of ammonia, and 1.8 moles of hydrogen exert a
pressure of 50 atmospheres at a certain temperature. Calculate the partial pressure of each
component in the mixture.

Solution:
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 = 0.6 + 0.8 + 1.8 = 3.2 𝑚𝑜𝑙𝑒𝑠
0.6
Partial pressure of 𝑁2 = 3.2 × 50 = 9.375 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
0.8
Partial pressure of 𝑁𝐻3 = 3.2 × 50 = 12.5 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
1.8
Partial pressure of 𝐻2 = × 50 = 28.125 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
3.2

2. 3.6 g of carbon dioxide and 4.8 g of oxygen were mixed in a one litre container. If the total
pressure of the mixture is 100 kPa, calculate the partial pressure of each gas.
3. A mixture of gases containing 30% carbon dioxide, 50% oxygen and 20% carbon monoxide
exerts a pressure of 1.01 × 105 𝑃𝑎. Calculate the partial pressure of each gas.

Liquefaction of a gas

When a gas is sufficiently cooled and then compressed, it condenses into a liquid.
Condensation of gases depends on two factors; intermolecular attraction and thermal/ kinetic
energy of the molecules.
The effect of condensation of a gas was investigated by T. Andrews (1869) using carbon dioxide
gas subjected to various pressures while changing the temperature.

At point A of the graph, carbon dioxide will be

in the gaseous state and as pressure is
gradually increased, the volume decreases
according to Boyle’s law.
At point B, the gas begins to liquefy. The
constant pressure along B to C is its saturated
vapour pressure. Along B to C the liquid is in
equilibrium with the gas.
Liquefaction is complete at point C (i.e. all the
gas has been change into a liquid).
Further increase in pressure beyond C has little
effect on the volume of the liquid formed (i.e.
liquids are not compressed as compared to
gases).

As temperature is progressively increased, the horizontal portion showing liquid⇌gas(vapour)

equilibrium becomes progressively shorter and above T3 it disappears.

3|Page
T3 represents the highest temperature at which it is possible to liquefy a gas by compression and it
is called the critical temperature.
Thus, Critical temperature is the temperature beyond which a gas cannot be liquefied no matter
how much pressure is applied.
Point E is called the critical point. This is the point above which a gas cannot be liquefied however
much pressure is applied.
Critical pressure is the least pressure which must be applied to liquefy a gas at its critical
temperature. The corresponding volume is known as the critical volume.

Assignment
1. (a) Define the term critical temperature.
(b) The diagram shows isothermals of a gas.

(i) On the diagram, indicate the following phases of the gas.

(ii) What is the critical temperature of the gas?
(iii) Which isothermal is in accordance with Boyle’s law?
(c) State;
(i) what the region ABC represents?
(ii) one condition necessary for liquefying a gas.
(iii) two factors necessary for liquefaction of a gas.

RELATIVE ATOMIC MASS

Masses of atoms are too tiny and often range from between 10-27 and 10-23 kg.

For example, the mass of a hydrogen atom is 1.627 × 10−27 Kg.

Since masses of atoms are very small, it is very difficult to obtain absolute/exact masses by
weighing on a kilogram scale.

The difficulty in measuring such tiny masses made scientists to obtain masses of atoms by
comparison with masses of another atom hence the term relative atomic mass.

Originally, hydrogen the hydrogen atom whose RAM is one unit was used as a reference scale thus
R.A.M was defined as the number of times a naturally occurring atom of an element is heavier than
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑎𝑛 𝑒𝑙𝑒𝑚𝑒𝑛𝑡
the hydrogen atom i.e. 𝑅𝐴𝑀 = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 .

4|Page
However, with scientific advancement, the hydrogen atom was dropped as a reference atom,
oxygen atom chosen and also later dropped and then carbon-12 atom introduced in 1962.

Thus R.A.M of an element is the number of times the mass of a naturally occurring atom of the
element is heavier than a twelfth of the mass of an atom of the carbon-12 isotope of carbon.

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑎𝑛 𝑒𝑙𝑒𝑚𝑒𝑛𝑡

Thus, we can write, 𝑅𝐴𝑀 = 1 .
×𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛−12 𝑖𝑠𝑜𝑡𝑜𝑝𝑒
12

On the carbon scale, the mass of carbon-12 isotope of carbon is taken as 12. Since the RAM is a
ratio, it has no units.

Mass spectrometer

This is an instrument used to obtain accurate masses of atoms. The instrument was invented by
F.W. Aston (1919) and has different types and forms depending on the sample being analysed.

The instrument has the following advantages;

 Requires a very small sample.
 It is quick (fast)
 Gives very accurate results.

The five essential parts of one of a mass spectrometer are;

1. Vapourisation chamber; where a solid or liquid sample is vapourised first.
2. Ionisation chamber; where the vapour formed is ionised into positive ions. Positive ions can
be formed in various ways and this can be by;
 heating using electrically heated tungsten filament.
 bombarding with fast moving and high energy electrons.
 passing a spark discharge through the sample.
3. Electric field (analyser); which attracts and accelerates the positive ions formed to a high and
constant velocity into the magnetic fields.
4. Magnetic field; which deflects the high speed positive ions into circular paths and focuses them
on the ion detector/collector according to their mass to charge ratio.
5. Collector (ion detector); this is where the deflected and focused positive ions fall and are sent
to the amplifier. The amplifier turns the positive ions received into sizeable electric current
which then operates a pen and draws a mass spectrum for the ions collected and detected.

5|Page
Mode of operation of the mass spectrometer.

The apparatus is evacuated in order to avoid interference by the air molecules.

The vapourised sample is then allowed into the ionisation chamber where it is subjected to a beam
of high energy electrons emitted from the hot filament to form positively charged gaseous ions.

The positive ions are accelerated to same velocity by strong electric field into the magnetic field
that deflects the ions according to their mass to charge ratio. The heavier ones are deflected least
and lighter ions are deflected most.

The strength of both the electric and magnetic fields are varied so that particular ions enter and
strike the ion collector/detector.

Electric current is produced when ions strike the collector. The magnitude of the electric current is
proportional to the relative percentage abundances of the ions.

The current produced is then amplified by the amplifier and recorded as a series of lines or peaks
called a spectrum. The number of peaks gives the number of isotopes present and the height of the
lines gives the relative percentage abundances of the isotopes.

Note:
A non-isotopic naturally occurring element will only show one peak/ line.
The relative atomic mass of the element is the average mass of its isotopes recorded.

The relative atomic mass (RAM) is then calculated from the expression;
𝐼𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠 × % 𝑎𝑏𝑢𝑛𝑑𝑎𝑐𝑒
𝑅𝐴𝑀 = ∑ ( )
100
Note:

6|Page
 For elements which exist as diatomic molecules e.g. chlorine and oxygen, the observed spectra in
the mass spectrometer will contain peaks or lines for both the separate atoms and molecules.
This is because the molecules break up into fragments. The number of peaks or lines depends on
the number of isotopes the element has.
For example, chlorine has two isotopes (i.e. 35Cl and 37Cl) and thus gives rise to five peaks or lines.
The five peaks are due to the following ions;

 35Cl+which corresponds to the mass at 35.

 37Cl+which corresponds to the mass at 37.
 [35Cl−35Cl]+ Which corresponds to the mass at 70.
 [35Cl−37Cl]+ Which corresponds to the mass at 72.
 [37Cl−37Cl]+ Which corresponds to the mass at 74.

Disadvantages of using a mass spectrometer

 Machine is very expensive to acquire.

 Samples which cannot be vapourised cannot be analyzed.

Other uses of a mass spectrometer

1. Determination of the relative molecular mass

2. Identification of compounds by comparing the spectra obtained with those in the data bank.
3. Used in forensic science e.g. in the identification of drugs, tracing suspects in a crime scene etc.

Relative abundance is the ratio of abundance of an isotope of an element in nature as compared to

the abundance of other isotopes of the same element in nature.

Examples:

1. The mass spectrum of neon (Ne) is shown below

(a) Calculate the relative atomic mass of

neon.
(b) Why does the spectrum show three
peaks?

Solution
𝐼𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠 ×% 𝑎𝑏𝑢𝑛𝑑𝑎𝑐𝑒
(a) 𝑅𝐴𝑀 = ∑ ( 100
)

7|Page
 (20 × 90.82) + (21 × 0.26) + (22 × 8.92)
𝑅𝐴𝑀 = = 20.2
100
(b) The three peaks show that Neon has three isotopes; 20Ne, 21Ne and 22Ne.

Note: If the detector current or intensity is given, sometimes you may be required to convert
them first to percentage abundance as shown in example 2 and 3 below. The total abundance is
always equal to 100%.

2. The mass spectrum of magnesium is shown below. Use it to determine the atomic mass of
magnesium.

Solution
𝑖𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦 ×𝑖𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠
𝑅𝐴𝑀 = ∑ ( 𝑡𝑜𝑡𝑎𝑙 𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦
)

Total intensity=100+12.8+14.4=127.2
(100 × 24) + (12.8 × 25) + (14.4 × 26)
𝑅𝐴𝑀 = = 24.3
127.2
Alternatively:
Total intensity=100+12.8+14.4=127.2
100
Percentage abundance of 24Mg= 127.2 × 100 = 78.62%
12.8
Percentage abundance of 25Mg= 127.2 × 100 = 10.06%
14.4
Percentage abundance of 26Mg= × 100 = 11.32%
127.2

𝐼𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠 × % 𝑎𝑏𝑢𝑛𝑑𝑎𝑐𝑒

𝑅𝐴𝑀 = ∑ ( )
100
(24 × 78.62) + (25 × 10.06) + (26 × 11.32)
𝑅𝐴𝑀 = = 24.3
100

8|Page
3. The table below shows the information from a mass spectrum of a lead sample.

Isotope Detector current(mA)

204 0.16

206 2.72

207 2.50

208 5.92

Calculate;
(i) the relative abundance of the different isotopes of lead in the sample.
(ii) the relative atomic mass of lead.

Isotopes

Various elements (except F, Na, Al, P, Mn, Co and As) possess atoms with different atomic masses
but same atomic number (number of protons). Such atoms are called isotopes.

Thus, isotopes are atoms of the same element with the same number of protons but different mass
numbers.

For example 35
17𝐶𝑙 and 17𝐶𝑙 are isotopes of chlorine while 6𝐶 and 6𝐶 are isotopes of carbon.
37 12 14

The occurrence of atoms with different relative atomic mass but the same atomic number and
chemical properties which are identical is called isotopy.

Isotopes have same chemical properties since they have the same number of electrons in the
outermost energy level. This therefore makes it difficult to separate isotopes by chemical means
and obtain their masses.

Due to the existence of isotopes, relative atomic masses are not whole numbers. This is because,
obtaining the mass of an atom of element involves averaging the masses of naturally occurring
isotopes of the element.

In averaging the isotopic masses, relative availability of the isotope is considered. The availability of
an isotope is usually expressed as relative abundance or percentage abundance.

This means that each isotope contributes to the whole relative atomic mass of an element.
𝐼𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠 × % 𝑎𝑏𝑢𝑛𝑑𝑎𝑐𝑒
𝑇ℎ𝑢𝑠, 𝑅𝐴𝑀 = ∑ ( )
100
Examples:

1. Copper has two isotopes, 63Cu and 65Cu. The relative abundances of the isotopes are 67.5% and
32.5% respectively. Calculate the relative atomic mass of copper.
Solution:
𝐼𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠 × % 𝑎𝑏𝑢𝑛𝑑𝑎𝑐𝑒
𝑅𝐴𝑀 = ∑ ( )
100
(63 × 67.5) + (65 × 32.5)
𝑅𝐴𝑀 = ( ) = 63.65
100
9|Page
2. The isotopes of chlorine are 35Cl and 37Cl. Calculate the relative abundance of each isotope of
given that the relative atomic mass of chlorine is 35.5.
3. Bromine has the following isotopes; 79Br and 81Br. Given that bromine has relative atomic mass
of 80, determine the percentage abundances of each isotope.
4. Iridium has the following isotopes; 191Ir and 193Ir. Given that Iridium has relative atomic mass of
192.2, determine the percentage abundances of each isotope.
[𝐴𝑛𝑠𝑤𝑒𝑟 = 40% 𝑎𝑛𝑑 60% 𝑟𝑒𝑠𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦]
5. The mass spectrum of choline shows peaks at 70, 72, and 74. The heights of the peaks are in a
ratio of 9:6:1 respectively. Calculate;
(a) the average atomic mass of chlorine.
(b) the relative abundance of 35Cl and 37Cl.

10 | P a g e