Physical Chemistry for Chemical Engineering 2020 - 2021 Dr.

Abdulmajed Alsaifi

Chapter (1)
Chemical Equilibrium

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Chapter (1) Chemical Equilibrium
Chemical Equilibrium:
• What does is mean to describe a chemical reaction as being in a state of dynamic
equilibrium?
➢ What are the characteristics and requirements of dynamic equilibrium?
• What does the equilibrium constant, K represent?
• How can we determine (quantitatively) the composition of a reaction mixture when it is at a
state of dynamic equilibrium?
• How do specific changes made to a system at equilibrium affect the equilibrium position?
➢ qualitatively understand changes
Dynamic Chemical Equilibrium:
• To date, we have mostly focussed on describing chemical reactions as going to completion:
AgNO3 (aq) + NaCl (aq) → AgCl (s) + NaNO3 (aq)
➢ identify limiting reactant calculate theoretical & percent yields
• For many chemical reactions, this discussion is not appropriate because they do not go to
completion.
• For these reactions we want to talk about:
➢ when they reach dynamic equilibrium [reactants] & [products] present at equilibrium
• Consider: NO2 (g) + NO2 (g) → N2O4 (g)
reddish-brown gas colorless gas
➢ put NO2 (g) in a sealed container at 25°C
➢ see decrease in intensity of brown color as NO2 is converted to N2O4
➢ contents of container never go completely colorless
∴ the reaction does not go to completion
➢ at some point the intensity of brown color stops changing
∴ the [NO2] is constant
➢ the system has reached a state of dynamic equilibrium

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

For a system at equilibrium:

• both forward and reverse reactions are occurring simultaneously
• rate of forward reaction must equal rate of reverse reaction
• OR Rateforward = Ratereverse
• concentrations of reactants and products remain constant with time
Changes in Rate and Concentration as a System Approaches Equilibrium:
• Consider the following reaction:
CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g)
(1) Initially, only the reaction CO + 3H2 → occurs. Because the concentrations of CH4 and
H2O are zero
(2) Later, as this reaction proceeds:
➢ the concentrations of CH4 and H2O increase, and the reaction
CH4 + H2O → begins.
➢ The rate of the reaction
CH4 + H2O → steadily increases,
➢ whereas the rate of the reaction
CO + 3H2 → decreases.
(3) Eventually, the two rates become equal.
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)
• Equilibrium is achieved at the point when:
➢ [H2], [CO], [CH4], and [H2O] are constant with time
➢ rate of CO + 3H2 → CH4 + H2O is the same as the rate of

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
CH4 + H2O → CO + 3H2

Position of Chemical Equilibrium:

• the equilibrium position refers to the relative amounts of reactants and products in the
system at the point of equilibrium
• a reaction with an equilibrium position that favors the products:
➢ [product] > [reactant] at equilibrium lies to the right
• a reaction with an equilibrium position that favors the reactants:
➢ [reactant] > [product] equilibrium lies to the left
The Equilibrium Constant, K:
• What is the quantitative relationship between [reactants] & [products] present in a system at
equilibrium?
➢ established by Guldberg & Waage in 1864.
➢ Law of Mass Action: concentrations of reactants and products in a mixture at equilibrium
always satisfy a specific, mathematic relationship.
Concentrations of Reactants & Products at Equilibrium:
• consider the reaction: 2SO2(g) + O2(g) → 2SO3(g)
➢ reaction run multiple times
➢ same temperature (T = 1000 K)
➢ initial concentrations of reactants changed
➢ equilibrium concentrations of all species determined

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

exp’t [O2]eq, M [SO2]eq, M [SO3]eq, M KC

1 0.390 0.660 0.0840
2 0.220 0.380 0.00360
3 0.110 0.110 0.00750
4 0.880 0.950 0.180
5 1.98 1.44 0.410

• there is no obvious trend in the concentration data until it is treated in this way:

exp’t [O2]eq, M [SO2]eq, M [SO3]eq, M KC

1 0.390 0.660 0.0840 0.0415
2 0.220 0.380 0.00360 0.0409
3 0.110 0.110 0.00750 0.0423
4 0.880 0.950 0.180 0.0408
5 1.98 1.44 0.410 0.0409

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
The Law of Mass Action:
• the concentrations of reactants and products in a mixture at equilibrium always satisfy a
specific relationship.
• for a reaction: aA + bB ⇌ cC + dD

• this is called the equilibrium expression.

• KC – the subscript “C” represents that this is the equilibrium constant in terms of molar
concentrations.
The Equilibrium Constant:

• typically unitless.
• concentrations used are relative to a standard molar concentration of 1M. dependent on
specific reaction.
• dependent on temperature.
• dependent on equilibrium composition.
• independent of initial concentrations.
Example:
Consider the following reaction at 500 K:
2NO(g) + O2(g) ⇌ 2NO2(g); KC = 6.9 x 105.
This reaction is allowed to reach equilibrium, and then analyzed and found to contain the
following concentrations: [O2] = 1.0 x 10–3 M, [NO2] = 5.0 x 10–2 M Write the equilibrium
expression for this reaction, and then determine the equilibrium concentration of NO(g).
Solution:
[O2] = 1.0 x 10–3 M, [NO2] = 5.0 x 10–2 M , KC = 6.9 x 105
• The equilibrium expression for this reaction
2NO(g) + O2(g) ⇌ 2NO2(g); KC = 6.9 x 105.
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
[𝑵𝑶𝟐 ]𝟐
𝐊𝐂 =
[𝑵𝑶]𝟐 .[𝑶𝟐 ]
𝟓 (𝟓.𝐱 𝟏𝟎−𝟐 )𝟐
𝟔. 𝟗 𝒙 𝟏𝟎 =
[𝑵𝑶]𝟐 .(𝟏.𝒙 𝟏𝟎−𝟑 )

𝟐𝟓 𝐱 𝟏𝟎−𝟒
[𝑵𝑶]𝟐 = = 3.62 x 10‒2
𝟔.𝟗 𝒙 𝟏𝟎−𝟐
[𝐍𝐎] = √𝟑. 𝟔𝟐 𝐱𝟏𝟎−𝟐 = 𝟏. 𝟗 𝐱𝟏𝟎−𝟏 𝐌
Magnitude of KC:
• What does the magnitude of KC tell you about a chemical reaction and it’s equilibrium
position?

• if KC > 1 . . .
➢ [products] > [reactants] equilibrium position favors products equilibrium position lies to
the right.
• if KC < 1 . . .
➢ [reactants] > [products] equilibrium position favors reactants equilibrium position lies to
the left.
Relationship Between Kinetics and Equilibrium: K and k:
• consider the equilibrium:

• when this system is at equilibrium:

➢ Rateforward = Ratereverse
• the rate laws:
➢ Rateforward = kfor[A2][B2]
➢ Ratereverse = krev[AB]2
➢ kfor[A2][B2] = krev[AB]2

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
• if kfor > krev
➢ KC > 1:
✓ forward reaction is favored equilibrium position lies to the right
• if kfor < krev
➢ KC < 1:
✓ reverse reaction is favored equilibrium position lies to the left
• typically, kfor ≠ krev
KC Values for Related Reactions:
• How does KC change if a chemical reaction is written in reverse?
• How does KC change if the stoichiometric coefficients of a chemical reaction are changed
(i.e. multiplied by n)?
• How do you determine KC for a chemical reaction if you can write it as the sum of 2 or more
chemical reactions?
Example (1):
• How does KC change if a chemical reaction is written in reverse?
• consider: H2(g) + I2(g) ⇌ 2HI(g); KC = 54
and: 2HI(g) ⇌ H2(g) + I2(g); KC1 = ???

And

• If you write a chemical equation in reverse, the new equilibrium constant is equal to the
reciprocal of the original equilibrium constant.
Example (2):
• How does KC change if the stoichiometric coefficients of a chemical reaction are changed
(i.e. multiplied by n)? consider:
H2(g) + I2(g) ⇌ 2HI(g); KC = 54
and: 2H2(g) + 2I2(g) ⇌ 4HI(g); KC2 = ???

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

And

• If the stoichiometric coefficients of a chemical reaction are multiplied by some factor, n, the
equilibrium constant for the reaction must be raised to the nth power.
Example (3):
• How do you determine KC for a chemical reaction if you can write it as the sum of 2 or more
chemical reactions?
• consider combining the following equations:
2P + 3Cl2 ⇌ 2PCl3; KC3
2PCl3 + 2Cl2 ⇌ 2PCl5; KC4
_____________________________________
2P + 5Cl2 ⇌ 2PCl5; KC = ???

• If a chemical reaction can be expressed as the sum of 2 or more chemical equations, the
equilibrium constant for the overall reaction is the product of the equilibrium constants for
the component reactions.
• Summary of K’s for Related Equations:

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Equilibrium Constant, KP:
• for gas phase reaction mixtures, we can consider the partial pressures of reactants and
products present at equilibrium.
• consider: H2(g) + I2(g) ⇌ 2HI(g)

• relationship between KC and KP for a reaction at a given temperature is:

KP = KC(RT)∆n
∆n = mol gas phase product – mol gas phase reactant
• KP = KC when ∆n = 0
Example (2):
• consider:
H2(g) + I2(g) ⇌ 2HI(g); KC = 54
KP = KC(RT)∆n
∆n = mol gas phase product – mol gas phase reactant
∆n = 2 mol – 2 mol = 0 mol
KP = 54 (RT)0 = 54 x 1 = 54
Example:
CH4 reacts with H2S to form H2 and CS2:
CH4(g) + 2H2S(g) ⇌ CS2(g) + 4H2(g)
Determine the value of KP for this reaction at 1000 K if the following equilibrium pressures
were measured:
PCH4 = 0.20 atm , PH2S = 0.25 atm , PCS2 = 0.52 atm , PH2 = 0.10 atm
Determine the value of KC for this reaction at 1000 K.
Example (2):
PCH4 = 0.20 atm , PH2S = 0.25 atm ,
PCS2 = 0.52 atm , PH2 = 0.10 atm
• CH4(g) + 2H2S(g) ⇌ CS2(g) + 4H2(g)
(𝐏𝐂𝐒𝟐 ).(𝐏𝐇𝟐 )𝟒
𝐊𝐏 = (𝐏𝐂𝐇𝟒 ).(𝐏𝐇𝟐𝐒 )𝟐

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
(𝟎.𝟓𝟐).(𝟎.𝟏)𝟒 𝟓.𝟐 𝒙 𝟏𝟎−𝟓
𝐊𝐏 = (𝟎.𝟐).(𝟎.𝟐𝟓)𝟐
= = 𝟒. 𝟏𝟔 𝒙 𝟏𝟎−𝟑
𝟏.𝟐𝟓 𝒙 𝟏𝟎−𝟐

KP = KC(RT)∆n
4.16 x 10‒3 = KC (0.0821 x 1000)2
4.16 x 10‒3 = KC (82.1)2
4.16 x 10‒3 = KC (6740.41)
KC = 6.17 x 10‒7
Heterogeneous Equilibria:
• heterogeneous equilibria – reactants and products are present in more than one phase
examples:
H2O(l) ⇌ H2O(g)
CO2(g) + C(s) ⇌ 2CO(g)
• concentrations of pure liquids and pure solids are constant and do not change
• bottom line – solids and liquids are not included in the equilibrium expression
• two very important examples for heterogeneous equilibria
(1) heterogeneous equilibria involving weak acids and/or weak bases:
HNO2(aq) + H2O(l) ⇌ H3O+(aq) + NO2–(aq)

(2) heterogeneous equilibria involving the solubility of ionic compounds:

Ca(IO3)2(s) ⇌ Ca2+(aq) + 2IO3–(aq)
KC = [Ca2+][IO3–]2
Predicting the Direction of Change: Q vs K
• How do you decide if a system is at equilibrium?
• OR If a system is not at equilibrium, does it proceed in the forward or reverse direction to
reach equilibrium?
• use “arbitrary initial concentrations” to calculate the reaction quotient, QC for the reaction:
aA + bB ⇌ cC + dD

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

• compare Q and K
➢ if Q = K: the system is at equilibrium
➢ if Q < K: the system is not at equilibrium the reaction proceeds in the forward
direction to reach equilibrium
➢ if Q > K: the system is not at equilibrium the reaction proceeds in the reverse
direction to reach equilibrium

Example:
Consider the following reaction:
2NO(g) + O2(g) ⇌ 2NO2(g); KC = 6.9 x 105
A 5.0 L vessel contains 0.060 mol NO, 1.0 mol O2, and 0.80 mol NO2.
Is this system at equilibrium?
If the system is not at equilibrium, does the reaction proceed in the forward or reverse
direction to reach equilibrium?
Process for Solving Equilibrium Problems: Using an Equilibrium (or ICE) Table:
• start with balanced chemical equation
• 3 rows for each gas or sol’n phase species:
➢ initial concentration or pressure.
➢ change (∆) in concentration or pressure as system moves to equilibrium.
➢ equilibrium concentration or pressure.
• consider the reaction:

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
2A(g) + B(g) ⇌ 3C(g)
[A], M [B], M [C], M
initial [ ] 1.00 M 2.00 M 0
∆[] – 2x –x + 3x
equil [ ] (1.00 – 2x) M (2.00 – x) M 3x M
notes:
• reactants A and B are consumed, so their Δ [ ] is –
• product C is formed, so it’s ∆ [ ] is +
• equil [ ]’s are the sum of the initial [ ] row and the ∆[ ] row
• if we start with true initial data – before any reaction has occurred, initial [product] = 0
Solution:
• consider the reaction:
2A(g) + B(g) ⇌ 3C(g)
[A], M [B], M [C], M
initial [ ] 1.00 M 2.00 M 0
∆[] – 2x –x + 3x
equil [ ] (1.00 – 2x) M (2.00 – x) M 3x M
What we don’t know:
• How much A and B will be consumed (and how much C will form) to get the system to
equilibrium?
• OR – we don’t know how [A], [B], and [C] will change as system approaches equilibrium
• ∴ define our unknown “x”
• consider the reaction:
2A(g) + B(g) ⇌ 3C(g)
[A], M [B], M [C], M
initial [ ] 1.00 M 2.00 M 0
∆[] – 2x –x + 3x
equil [ ] (1.00 – 2x) M (2.00 – x) M 3x M

What we do know:
• stoichiometry of how A and B combine to form C for every 1 mol B consumed, 2 mol A
consumed & 3 mol C form
• OR – if x mol B are consumed, 2x mol A will be consumed and 3x mol C will form.

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
What we do know:

Equilibrium Calculations:
• Determine the equilibrium composition of a reaction: determine the concentration (or
pressure) of each species present in the system when equilibrium is established
• Example:
SO2(g) + NO2(g) ⇌ SO3(g) + NO(g) KC = 3.75
1.24 mol SO2(g) and 0.750 mol NO2(g) are combined in a 2.50 L flask, and the reaction is
allowed to reach equilibrium. Determine the concentration of each species present at
equilibrium.
Solution:
SO2(g) + NO2(g) ⇌ SO3(g) + NO(g) KC = 3.75
[SO2 (g)], M [NO2 (g)], M [SO3 (g)], M [NO(g)], M
initial [ ] 0.496 M 0.300 M 0M 0M
∆[] –x –x +x +x
equil [ ] (0.496 – x) M (0.300 – x) M xM xM

• Quadratic Equations and the Quadratic Formula

• quadratic equation: ax2 + bx + c = 0
• quadratic formula:

• you will get 2 mathematically correct answers for x only one is the right answer for our
problem the other is the “extraneous root”

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
• back to our example:
Solution:
• SO2(g) + NO2(g) ⇌ SO3(g) + NO(g) KC = 3.75
[SO2 (g)], M [NO2 (g)], M [SO3 (g)], M [NO(g)], M
initial [ ] 0.496 M 0.300 M 0M 0M
∆[] –x –x +x +x
equil [ ] (0.496 – x) M (0.300 – x) M xM xM

• using the quadratic formula: x = 0.847 (extraneous) or 0.240

• So, at equilibrium:
[SO2] = 0.496 – x = 0.256 M
[NO2] = 0.300 – x = 0.060 M
[SO3] = [NO] = x = 0.240 M
Equilibrium Calculations
• Determine the equilibrium composition of a reaction using pressure data and KP
• example: CO(g) + H2O(g) ⇌ CO2(g) + H2(g); KP = 4.24
• A vessel is filled with 12.0 atm CO (g) and 12.0 atm H2O (g) at 800 K, and the reaction
progresses until equilibrium is established.
• Determine the pressure (in atm) of each species present in the reaction mixture at
equilibrium.

Solution:
CO(g) + H2O(g) ⇌ CO2(g) + H2(g); KP = 4.24
PCO , atm PH2O , atm PCO2, atm PH2, atm
initial P 12.0 atm 12.0 atm 0 atm 0 atm
∆P –x –x +x +x
equil P (12.0–x) atm (12.0–x) atm x atm x atm

solution: x = 8.07

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
at equilibrium: PCO = PH2O = 3.93 atm; PCO2 = PH2 = 8.07 atm
Le Chatelier’s Principle:
• When a stress is applied to a system at equilibrium, the equilibrium position will shift in the
direction that relieves the applied stress.
• stresses include: changes in concentration or pressure of reactants or products by the
addition or removal changes in pressure as a result of changes in volume of container
changes in temperature (value of K will change) addition of a catalyst
(1) Effect of Changes in Concentration on Equilibrium Position:
• If the concentration or pressure of a substance is increased by the addition of more reactant
or product . . .
• For the reaction:
aA + bB ⇌ cC + dD
[𝐶]𝑐 .[𝐷]𝑑
𝐾𝐶 = [𝐴]𝑎 .[𝐵]𝑏

➢ the equilibrium position will shift in the direction that consumes the added substance.
➢ OR the equilibrium position will shift away from the increased concentration
• If the concentration or pressure of a substance is decreased by the removal of reactant or
product . . .
➢ the equilibrium position will shift in the direction that replenishes the removed substance
➢ OR the equilibrium position will shift toward the decreased concentration
(2) Effect of Changing Pressure on Equilibrium Position:
• There are 3 ways to change the pressure of a chemical reaction system:
1. add or remove a gas phase reactant or product
➢ recall that Preactant or Pproduct are related (through PV = nRT) to molar concentration
➢ the result of adding or removing gas phase reactant or product can be predicted
according to the guidelines stated above for effect of changing concentration.
2. add an inert gas

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
➢ the addition of an inert gas to a system changes the total pressure of the system,
but not the partial pressures (i.e. changing concentrations) of gas phase reactants
or products
➢ the result is no change in equilibrium position
3. change the volume of the container !
➢ recall that P and V are inversely proportional to one another !
➢ If the equilibrium is disturbed by changing the volume of the container, Le Chatelier’s
Principle predicts:
✓ An increase in pressure resulting from reduced container volume will bring about
net reaction in the direction that decreases the number of moles of gas phase species
(i.e. the volume of the chemical system will decrease).
✓ A decrease in pressure resulting from increased container volume will bring about
net reaction in the direction that increases the number of moles of gas phase species
(i.e. the volume of the chemical system will increase).
(3) Effect of Changing Temperature on Equilibrium Position & K:
• The temperature dependence of the equilibrium position and the value of the equilibrium
constant is dependent on the sign of ∆H of the reaction.
1. The equilibrium constant for an exothermic:
➢ reaction will decrease as temperature increases;
 equilibrium position will shift to the left as temperature increases.
2. The equilibrium constant for an endothermic:
➢ reaction will increase as temperature increases;
 equilibrium position will shift to the right as temperature increases
(4) Effect of a catalyst on equilibrium position:
• The addition of a catalyst does not effect on the equilibrium position of a reaction – only the
rate at which the system reaches equilibrium.

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

Chapter (2)
Chemical Kinetics

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Chapter (2) Chemical Kinetics
Chemical Kinetics:
• Chemical kinetics is defined as the branch of chemistry concerned with rates and
mechanisms of chemical reactions. It studies of the factors that affect the rates of chemical
reactions.
Reaction Rates and Their Measurement:
• In general, the rate (or speed) of any chemical reaction can be expressed as the ratio of the
change in the concentration of a reactant (or product) to a change in time. The rate of
chemical reaction is usually expressed in moles per liter per second (mol/L.s).
concentration change
Rate of reaction =
time change
For the following reaction:
A →B
• During the progress of a reaction, concentrations of the reactants gradually decrease, while
those of the products increase as the time increases. This can be illustrated in curve
(Fig.3.1).
12
moles A or B

10
8 moles A
6
moles B
4
2
0
0 50 100

time (min)

• The rate of this reaction at any moment can be expressed as follows:

Rate of reaction = Amount of A consumed

Time interval
Amount of B produced
or Rate of reaction =
Time interval
• The rate of a reaction can be expressed as appearance of B and also can be expressed
as the disappearance of A as a function of time.

Rate = Δ [B] (Appearance of B)

Δt
or Rate = − Δ [A] (Disappearance of A)
Δt

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
• The rate may be obtained from the slope of the tangent to the plot of concentration of the
species with time (Fig. 3.1). The rate of reaction from concentration, C1 to C2 during the
time interval from t1 to t2 will be expressed as:

Rate of disappearance of A = − [A]t 2 −[A]1

−t 2 1

Rate of appearance of B = [B]t 2 −[B]1

−t
2 1

• The minus sign indicates that the concentration of A is decreasing with time. A minus
sign is always used whenever reactants are employed to express the rate.
• We can calculate the average rate for any time interval involved in the reaction.
Example:
Given the following data:
CH3OH (aq) + HCl (aq) → CH3Cl (aq) + H2O (l)
[HCl] (M) 1.85 1.58 1.36 1.02
Time (min) 0.0 54.0 107.0 215.0
what is the average rate of HCl over the time interval from 54.0 min to 215.0 min?
Solution:
[HCl]54 min = 1.58 M , [HCl]215 min= 1.02 M

Average rate = − Δ[HCl]

Δt
[HCl]215 min − [HCl]54 min
=−
215 min − 54 min
(1.02 − 1.58)
=−
215 min − 54 min
= 0.56
161
= 3.5 x 10-3 M/s
Reaction Rates and Stoichiometry:
• The coefficients in the equation allow us to construct the conversion factors. Thus, each
term in the rate equation is multiplied by the reciprocal of the stoichiometric coefficient
from the balanced equation, which equalizes the rates.
• In general, consider the following reaction:
aA + bB → cC + dD
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
• The rate of a chemical reaction is proportional to the concentration of the reactants,
but not necessarily all of the reactants.

Rate = − 1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]

a . Δt = − b . Δt = c . Δt = d . Δt

• This equation can be used to establish the relationship between rate of change of one
reactant or product to another reactant or product.
Notes:
• The notation [A] /t means “change in concentration of A with time.
• The minus sign for a reactant indicates a decrease in concentration with time, i.e., the
reactant disappears.
• The rate of appearance of C is ( ac ) times the rate of disappearance of A and ( c ) the rate of
b
disappearance of B.
For the following reaction:
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
• The relationships between rates of change of the reactants and products are:

Rate = − 14 . Δ[NH3 ] = − 15 . Δ[O2 ] = 14 . Δ[NO] = 16 . Δ[H2O]

Δt Δt Δt Δt
In this reaction, the ratio of NH3 to NO is 4:4 and the ratio of NH3 to O2 is 4:5.
Thus, the rate of disappearance of NH3 is the same as the rate of appearance of NO and is ( 4 )
5
times the rate of disappearance of O2.
Example:
If the rate of decomposition of N2O5 in the following reaction at a particular instant is 4.2 x
10–7 M /s, what is the rate of appearance of NO2?
2N2O5(g) → 4NO2(g) + O2(g)
Solution:
The rate of appearance of NO2 = ( 4 ).(rate of disappearance of N2O5
2
= ( 4 ) x 4.2 x 10–7 M/s
2
= 8.4 x 10–7 M/s
Exercise:
How is the rate of disappearance of N2O5 related to the rate of appearance of NO2?

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Law of Mass Action:
• Law of mass action states that the rate of a reaction is proportional to the product of the
concentrations of the reactants each raised to the power equal to the number of the
molecules of the reactant involved in the chemical equation. In generalized expression,
the rate of the following reaction:
A + B → products
Rate  [A]m .[B]n
or Rate = k [A]m .[B]n
where k is rate constant, m molecules of A and n molecules of B.
Rate Law:
The mathematical expression relating the concentrations of reactants to the reaction rate is
termed the rate equation or rate law.
Rate of a chemical reaction is determined experimentally and depends on:
1. Nature of the reactants:
2. Concentration of the reactants:
As concentration of reactants increases the rate of reaction generally increases
3. Temperature:
4. Presence or absence of a catalyst:
A catalyst is a substance that increases the rate of a reaction without being
consumed in the reaction
• The rate expression for the chemical reaction may not generally be derived from an
inspection of the balanced chemical equation of the overall reaction.
• Consider the following reaction:
xX + yY → products
The expression of the rate law is:
Rate = k [X]p.[Y]q
It shows how the reaction rate depends on concentration of each reactant.
Where:
k = specific rate constant (proportionality constant) at given temperature.
p =order of reaction for constituent X (0, 1, 2…)
q = order of reaction for constituent Y (0, 1, 2...)
 Overall reaction order = p + q
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Notes:
• If the order of reaction of a given reactant is “0”, then the rate of the overall reaction is not
dependent on the concentrations of that reactants.
• If the order of reaction of a given reactant is “1”, then a change in the concentration of that
reactant will have a proportional change on the overall reaction rate.
If the concentration of the reactant is doubled the rate of the reaction will double.
Example:
C4H9Cl + NaOH → C4H9OH + NaCl
t-Butyl Chloride t-Butyl Alcohol
Rate = k [C4H9Cl]1.[NaOH]0
= k [C4H9Cl]
The reaction is dependent only on the concentration of t-butyl chloride. Additional
NaOH has no affect.
The overall reaction order of this reaction is “1” (1 + 0 = 1)
• If the order of reaction of a given reactant is “2”, then a change in concentration of that
reactant changes the overall reaction rate by a factor of (22).
Example:
If the concentration of the reactant is doubled the rate of the reaction will quadruple.
• Usually the powers of concentrations in the rate law are different from coefficients in the
balanced equation.
Example:
Below some data collected in a series of experiments on the reaction of nitric oxide with
bromine at 27oC:
2NO(g) + Br2(g) → 2NOBr(g)

Experiment Initial Concentrations Initial Rate of Formation

(mol/L) of NOBr (M/s)
NO Br2
1 0.10 0.10 12
2 0.10 0.20 24
3 0.10 0.30 36
4 0.20 0.10 48
5 0.30 0.10 108

Determine the rate law for the reaction and compute the value of the rate constant.
Solution:
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
The rate law for the reaction will have the form:
Rate = k [NO]x.[Br2]y
To determine each exponent, we will study how the rate changes when the concentration of
one reactant varies while that of the other reactant stays the same. For instance, when the NO
concentration is held constant, we can see how changes in the Br 2 concentration affect the rate
and thereby determine what y must be. The value of x is determined in a similar way. With
this strategy in mind, let's study the data.
At constant concentration of NO: At constant concentration of Br2:
In experiments 1 to 3, the In experiments 1 and 4, the
concentration of NO is constant and concentration of Br2 is constant and
the concentration of Br2 is varied. the concentration of NO is varied.

R1 = 12 [Br2]1 = 0.10 R1 = 12 [NO]1 = 0.10

R2 = 24 [Br2]2 = 0.20 R2 = 48 [NO]2 = 0.20

− 0.30 = y (− 0.30) − 0.60 = x (− 0.30)

y=1 x=2

The rate law is:

Rate = k [NO]2.[Br2]
The rate constant can be evaluated using the data from any of these experiments. Working
with experiment 1, we have
12 = k (0.10)2.(0.10)
k= 12
1.0x10−3
= 1.2 x 104 L2 mol–2 s–1
Molecularity of a Reaction:
• Chemical reactions may be classed into two types:
(a) Elementary reactions:
An elementary reaction is a simple reaction which occurs in a single step.

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(b) Complex reactions:
A complex reaction is that which occurs in two or more steps. The slowest step is the
rate – determining step of the reaction.
• Molecularity of a reaction may be defined as the number of molecules or ions actually
taking part (or colliding) at a particular moment, in a single – step chemical reaction or a
step of the reaction.
• Accordingly, reactions may be termed unimolecular, biomolecular, and trimolecular.
For example:
N2O5 →NO2 + 12 O2 (unimolecular)
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH (bimolecular)
2SO2 + O2 → 2SO3 (trimolecular)
• Molecularity is always a whole number and never in fraction or zero.
• The knowledge of molecularity will further help us for understanding order of reaction.
Order of Reaction:
• Order of reaction is the sum of the exponents (powers) of the molar concentrations of the
reactants in the rate equation of the reaction.
For example, the rate of the following reaction is:
mA + nB → products
• in a one – step simple reaction:
Rate = K [A]m.[B]n
Order of reaction = m + n
• If the reaction is complex:
Rate = K [A]a.[B]b
Where a and b are different from m and n.
Order of reaction = a + b
We have seen in a proceeding section that a and b may be whole numbers, fractions or zero.
Molecularity Versus Order of Reaction:
• The term molecularity is often confused with order of a reaction. The total number of
molecules or atoms which take part in a reaction as represented by the chemical equation is
known as the molecularity of reaction.

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
• The sum of the powers to which the concentrations are raised in the rate law is known as
the order of reaction.
First – Order Reactions:
Consider the following reaction:
A Products
We can write a general expression for the rate equation for a first – order reaction by
representing the concentration of the reactant by the symbol [A]. Then:
Rate = k.[A] (3.1)
This rate equation can be expressed in terms of the rate of decrease in the concentration of A:

−
Δ[A] = k [A]
Δt
Rearrangement gives:
Δ[A] = Δt . k
− (3.2)
A
Which may be written in its differential form as following?

−
d[A] = k dt (3.3)
A
The equation (3.3) is integrated to give:

log  [A]o  = k t (3.4)

 [A]  2.303
where [A]o is the initial concentration of A at time zero, [A] is the concentration of A at time
t, and k is the rate constant.

log [A] = − k t + log [A]o (3.5)

2.303
Equation (3.5) is in the form of an equation for a straight line. If log [A] is plotted against t, a
straight result with a slope equal to − k and intercept of log [A]o.
2.303

Figure (3.2). A plot of the

logarithm of reactant, log [A]
Slope = − k/2.303
versus time, t , for first – order
log [A]

reaction. For any first – order

reaction a plot of this type is a
straight line with slope equal to
( ) and intercept of log [A]o.

Time, t
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Half – life (t½):
The time required for half reactant to react is known as the half – life of the reaction, t½.
The equation of half – life for first – order reaction is:
t 1 / 2 = 0.693
k
(3.6)
Notice that the half – life of given first – order reaction is a constant that is independent of the
concentration of the reactant.
Second – Order Reaction:
The following are examples of second – order reactions. The corresponding rate equations are
shown beside the equations for the reactions.
1. 2No2(g) →2 NO(g) + O2(g)
Rate = k [NO2]2 (3.7)
2. NO(g) + O3(g) → NO2 (g) + O2(g)
Rate = k [NO][O3] (3.8)
We can see, therefore, that two general expressions can be written for rate equations for
second – order reactions:
Rate = k [A]2
Rate = k [A][B]
We will discuss only the first type of rate equation, which is the simpler of the two to handle
mathematically. It can be used to describe rate equations for second – order reactions in which
there is only a single reactant (such as the reaction shown in Equation (3.7). It can also be
used to handle cases in which there are two different reactants (such as that shown in Equation
(3.8) but both reactants are present in the same concentration.
The differential form of the rate equation is:
d [A]
− = k dt
[A]2
By integration this equation can be converted into:
1 1
− =kt (3.9)
[A] [A]o
where [A]o is the initial concentration of A (at time = 0), [A] is the concentration of A at time
= t, and k is rate constant.
By rearranging above equation:

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
1 1
=k t+ (3.10)
[A] [A]o
Comparison of Equation (3.10) to the general equation for a straight line :
Y= mx + b
1
reveals that the curve that results when is plotted against t is a straight line with a slope
[A]
1
equal to (k) and an intercept of .
[A] o

Figure (3.3). A plot of 1/[A],

versus time, t, for a second-order
reaction for which rate = k[A]2. 1 Slope = k
For any second-order reaction of [A]
this type of 1/[A] vs. t is a straight
line with slope equal to(k) and an
intercept of .

Time, t
Half – life of Second Order:
We can find an expression for the half-life of a of a second-order reaction of this type in the
following way. Since half of the original quantity of A has been used at t1/2:
[A] 0
[A] = (3.11)
2
Hence, from Equation (3.9):
1 1
− = k t1/ 2
[A] o / 2 [A] o

2 1
− = k t1/ 2
[A] o [A] o

1
= k t1/ 2
[A]o

1
t1 / 2 = (3.12)
k [A] o

Notice that the half-life of this type of reaction is not independent of the concentration of
reactant. The half-life of a specific first-order reaction is the same no matter what initial

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concentration of reaction is used. The half-life of a specific second-order reaction, however, is
variable and depends upon the initial concentration of reaction.
Zero-Order Reactions:
The rate of a zero –order reaction is independent of reactant. In general,
Rate = k [A]0 (3.13)
and since [A]0 = 1
 Rate = k (3.14)
The decomposition of certain gases on the surfaces of solid catalysts is an example of zero –
order reaction. The catalyst is written over arrow in the chemical equation:
Ni
CH2==CH2 + H2 ⎯⎯→ CH3CH3
The differential form of the rate equation for zero – order reaction is:

−
d [A] = k (3.15)
dt
This equation is integrated to give:
[A]o – [A] = k.t (3.16)
or [A] = – k.t + [A]o (3.17)
where [A]o is the initial concentration of A at time zero, [A] is the concentration of A at time
t, and k is the rate constant.
Equation 3.5 is in the form of an equation for a straight line. If [A] is plotted against t, a
straight result with a slope equal to (− k) and intercept of [A]o.

Figure (3.4). A plot of concentration

of reactant, [A], versus time, t, for a
Slope = − k
zero order reaction for which rate = k. [A]
For any zero-order reaction a graph of
this type is a straight line with a slope
equal to (− k) and intercept of [A]o.
Time, t
Half –Life of Zero − Order Reaction:
An equation for the half –life of a zero-order reaction can be obtained from equation (3.16) at
t1/2,
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
[A] = ½ [A]o, hence:
k t½ = [A] − 12 [A]o
[A]o
t1/ 2 = (3.18)
2k
Effect of Increase of Temperature on Reaction Rate:
It has been found that generally an increase of temperature increases the rate of a reaction.
As a rule, an increase of temperature by 10oC doubles the reaction rate. From Arrhenius
equation:
d lnk Ea
= (3.19)
dT RT 2
In this equation, k is the rate constant, T the absolute temperature, R the gas constant in
calories or joule and Ea is a constant with respect to temperature. The minimum energy
which the molecules must absorb before the reaction can take place is known as the
energy of activation (Ea). Integration equation (3.19) gives the result:
Ea
ln k = − + constant (3.20)
RT
The constant in equation (3.20) is found to be (ln A). The factor A is known as the frequency
factor. Rewriting equation (3.20) as:
− Ea
log k = + log A (3.21)
2.303 RT

According to this equation, a plot of log k versus ( 1 ) should be a straight line with a slope (
T
− Ea
) and intercept (log A) as shown in Fig.3.5.
2.303 R

Example:
The values of the rate constant (k) for the reaction:
2N2O5 (g) → 4NO2(g) + O2(g)
were determined at several temperature. A plot of lnk
We can calculate the value of Ea from the values of k at two temperatures by using the
following equation:
k  E a  T2 − T1 
log 2  =  
 1
k 2.303 R  2 1 
T T
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

Chapter (3)
Colligative Properties and Colloid Solutions

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi
Chapter (3) Colligative Properties and Colloid Solutions

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

Colloid Solutions:
Colloid system:
• A colloid system is a type of mixture in which one part is dispersed constantly
throughout another.
• Colloid systems are usually formed when one part is dispersed through another, but does
not combine to form a solution.
• Therefore, there are many types of colloidal systems that depend on the form of the two
parts mixed together.
• A colloidal system contains two separate phases:
➢ a dispersed phase (or internal phase) and
➢ a continuous phase (or dispersion medium).
• The part which is dispersed is known as the dispersed phase and is suspended in the
continuous phase.
Classifying Colloids
A common method of classifying colloids is based on the phase of the dispersed substance
and what phase it is dispersed in. The types of colloids includes sol, emulsion, foam, and
aerosol.
1. Sol is a colloidal suspension with solid particles in a liquid.
2. Emulsion is between two liquids.
3. Foam is formed when many gas particles are trapped in a liquid or solid.
4. Aerosol contains small particles of liquid or solid dispersed in a gas.
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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

System Minor phase Major phase Products

Sol Solid Liquid Raw custard, unset jelly
Gel Liquid Solid Jelly and jam
Emulsion Liquid Liquid Mayonnaise, milk
Solid emulsion Liquid Solid Butter, margarine
Foam Gas Liquid Whipped cream, whisked egg white
Solid foam Gas Solid Meringue, bread, cake, ice cream

Hydrocolloid:
• When the dispersion medium is water, the collodial system is often referred to as a
hydrocolloid.
• For example, Jello powder mixed in with water creates a hydrocolloid.
• A common use of hydrocolloids is in the creation of medical dressings.
Tyndall Effect:
• An easy way of determining whether a mixture is colloidal or not is through use of the
Tyndall Effect.
• When light is passed through a colloidal solution, the substance in the dispersed phases
scatters )‫ (يبعثر‬the light in all directions, making it appear cloudy.
Stabilization of Colloids:
• The colloid is said to be stable when particles remain suspended in the solution without
settling down.
• Stability is hindered by aggregation and sedimentation phenomena, which are driven
by the colloid’s tendency to reduce surface energy.
• In order to stabilize the colloidal system, we need to reduce the interfacial tension
between the colloidal particles.

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Physical Chemistry for Chemical Engineering 2020 - 2021 Dr. Abdulmajed Alsaifi

Mechanisms for Stabilization:

The two main mechanisms for stabilization against aggregation.
• Electrostatic stabilization is based on the mutual repulsion of like electrical charges.
In general, different phases have different charge affinities, so that an electrical
double layer forms at any interface. Small particle sizes lead to enormous surface
areas, and this effect is greatly amplified in colloids.
• Steric stabilization consists in covering the particles in polymers which prevents the
particle to get close in the range of attractive forces.

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