Collision Theory of Reaction Rate

In collision Theory, a reaction takes place when molecules come in contact (collides) with one another

The rate of reaction is explained in terms of the energy of activation of the atom e.g consider a
bimolecular reaction where

A + B Product

Rate of reaction is given by k=Zq where z is the number of collision per second and q is the fraction of
the molecule which are activated. The value of z and q can be determined by kinetic energy.

Example : HI H2 + I2

Z11=½√2 * πr² * v(n’)² ––– (1) (when the reacting molecule are not alike

r = the collision diameter

n’ = the number of molecules per collision

Average velocity of colliding molecules = V = √8RT/2M

2r²(n’)8RT/2M

Z12=n¹-n²(r12)²√2πRT/μ

r1,2=r1+r2/2 the mean diameter of the colliding molecules

μ=m1m2/m1+m2 the Average molecular weight of two different molecules

The fraction of the molecule having different activation is given as n’/n=e^-Ea/RT ; K=Ze^Ea/RT where it
is a gaseous Reaction .

Exercise : Consider a Reaction 2HI(g) H2 + I2(g) at 556k, the quantity of the hydrogen Iodide (g) is 1mol
per litre. The energy of activation Ea is ?

IDEAL AND NON IDEAL SOLUTION

Solute + Solvent  solution [gas, liquid or solid]

An ideal solution obeys Raoult’s law

Psolution= Xsolute + Psolvent

Xsolute= No of mole of solvent/no of mole of solvent + no of mole of solution

For substance to be ideal the partial pressure of the solution must be equal to the total pressure

Examples of ideal solution

 N-hexane (C6H14) and n-heptane (C7H16)

 Benzene and toluene
Ideal solution must have the same component i.e structure and intermolecular forces

Non ideal solution does not obey Raoult’s law e.g

 They have different structure and intermolecular force or bond

 Their total enthalpy is equal to zero e.g HCl3 (chloroform) and benzene

A solution comprises of solute and solvent

Liquid-liquid solution are of two types ideal and non ideal

The above classification has been made possible by Raoult’s law

RAOULT’S LAW states that the vapour pressure of the pure solvent above a solution is equal to the
vapour pressure of the pure solvent at the temperature scaled by the mole fraction of the solvent.

Vpsolvent =Vppure solvent

Raoult’s law also states that the mole fraction of the solute component is directly proportional to its
partial pressure

Psolution= Xsolute + Psolvent

Where Psolution is the vapour pressure of the solution , Xsolute is the

According to the above law, when a substance is dissolved in a solution, the vapour pressure of a
solution decreases as a result of the ole fraction of the amount of dissolved solute present and the
original vapour pressure of the pure solvent. Also Raoult’s law only works for solute which do not
change it’s nature when dissolved I.e do not ionize or associate

IDEAL SOLUTION

These are solutions that obey Raoult’s law at any range of concentration and at all temperature. They
are obtained by mixing two ideal component (solute and solvent)with similar molecular size and
structure. In addition, solution can be termed ideal, if the intermolecular forces of attraction between
two liquids (A and B) are nearly equal

Vp. Xa =1x Xa=0

Xb= 0. Xb =1
Definition of some important terms

Mole fraction : the mole fraction (x) of a solution is the ratio of the number of mole that component to
the total number of mole of all components in the solution

Xa= na/ntotal where Xa is the mole fraction of component A and na is the no of mole o component A, ntotal is
the total no of mole of all component present in the solution

Vapour pressure is the pressure exerted by a vapour with it’s condensed plane (solid or liquid) in closed
system at a given temperature

CHARACTERISTICS OF IDEAL SOLUTION

 They obey Raoult’s law i.e the partial pressure of component A and B In a solution will be
PA= Pa”Xa and Pb=Pb*Xb

Where Pa and Pb is the vapour pressure of A and B respectively, Xa and Xb respectively is the mole fraction
of component A and B

 The solute-solute interaction and solvent-solvent interaction is almost similar to the solute-
solvent interaction
 The enthalpy of mixing two components should be zero i.e ∆mixH =0. This implies no heat is
released or absorbed during mixing of the pure component to form an ideal solution
 The volume of the mixing is equal to zero ∆mixV=0

This explains that the total volume solution is exactly same as the sum of the volume o solute and
solution, it also signifies that there will be contraction or expansion in the dissolution of liquid

CHARACTERISTICS OF NON IDEAL SOLUTUON

 The solute-solute and solvent-solvent interaction are different from that of the solute-
solvent interaction
 ∆mixH≠0 i.e there will be some expansion or contraction in the dissolution of liquids

TYPE OF NON IDEAL SOLUTUON

 Non ideal solution +ve derivative fron Raoult’s law

This occurs when the vapour pressure of the component is greater than that what if expected in law.
Example of such solution are ethanal and water, Acetone and Benzene etc.

 Non ideal solution with -ve derivation from Raoult’s law

This occurs when the total vapour pressure is less than what it should be according to Raoult’s law.
Examples are HCl and water, HNO3 and H2O, chloroform and benzene

Exercise

 1.5 moles of Chery kool-Acid are added to a pitcher containing 2litres of water on a nice day
at 25°c. The vapor pressure of water alone is 238mmHg at 25°c, what is the new vapor
pressure of kool-Acid

Solution

PH2O =238mmHg, convert the litre of mole to moles 1l= 1000ml =1000g

No of mole = mass ÷ molar mass (H2O =18g/mol) , No of mole = 1000/18= 111moles

XH2O = moles of H2O ÷ moles of H2O+ moles of cherry kool-Acid

XH2O=111/111+1.5= 0.97mol

Raoult’s law  Pkool-acid =XH2O PH2O ; Pkool-acid= 0.97×23.8=23.5mmHg


 Calculate the vapour pressure of a solution made by dissolving 50g of glucose in 500g of
water. The vapour pressure of pure solvent is 47.1torr at 37°c

Solution

Nwater =500÷18=27.78mol Nglucose=50÷180=0.278mol

Xsolvent=Nwater/Nwater+Nglucose = 27.78/27.78+0.278=0.99

Psolution=Xsolute Psolvent ; Psolution= 0.99×47.1=46.629torr

COLLIGATIVE PROPERTIES

There are the physical changes that results from adding solute to a solvent . It only applies to solution
and depends on how many solute particles are present as well as the solvent amount but do not
depend on the type of solute particles

They are

 Towering of vapour pressure

 Elevation of boiling point
 Depression of freezing point
 Osmotic pressure
RAOULT’S LAW AND COLLIGATIVE PROPERTIES

The effects of Raoult’s law is that saturated vapor pressure of a solution is going to be lower than that
ofpure solvent at any given temperature

A phase diagram

It shows that solids are stable under High pressure and low temperature , liquid are stable under
average pressure and temperature condition while gasses are stable at low pressure and high
temperature

Phase diagram for water

Phase diagram showing the effects of lowering vapour pressure

The introduction of non volatile solute tends to lower vapour pressure of the solvent in a solution which
also leads to the elevation of boiling point and depression freezing point

Lowering vapor pressure ; the vapour pressure of a volatile solvent above a solution containing a non
volatile above a solute is proportional to the solvents concentration in the solution. This relationship is
expressed quantitatively by Raoult’s law which states that the partial pressure exerted by solvent vapour
above the solution is equal to the mole fraction of solvent multiplied by the vapour pressure of the pure
solvent

Psolution = Xsolvent Psolvent or ∆P=Psolution - Psolvent

Exercise

 The vapour pressure of water at 80°c is 335torr. Calculate the vapour pressure of an aqueous
solution made by dissolving 50g of ethylene glycol in 50g of water, what is the vapour pressure
lowering of water in the solution
 Glycerine is a non volatile, non electrolyte with density of 1.26g/mol at 25°c, calculate the
vapour pressure at 25°c of a solution made by adding 50ml of glycerine to 500ml of water . The
vapour pressure of water is 23.8 torr and it’s density is 1.00hg/mol
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