Reading assignment:

TOPIC: CHEMICAL KINETICS, Rates Of reaction, Chemical equilibrium, ionic equilibrium

THERMOCHEMISTRY: units of heat, specific heat
As a basis for understanding the topics and its application, make your notes based on the following
guide questions: DO NOT INCLUDE THE FORMULA STATED. THE APPLICATIONS ARE THE SAMPLE
PROBLEMS AND ANSWERS THAT YOU CAN USE TO UNDERSTAND YOUR ASSIGNMENTS.
Write you answer the guide questions. Considered as written works.
WHAT IS/define/describe
1. Chemical kinetics
2. Rates of reaction
3. Collision theory
4. Factors that influence reaction rates
a. Application of each factor
5. Chemical equilibrium/ equilibrium constants
a. Equilibrium constant expression, Keq
i. Equilibrium constant, Kc
ii. Importance of knowing the magnitude of equilibrium constants
b. Le Chatelier’s Principle
i. Factors affecting systems at chemical equilibrium
ii. Application of Le Chatelier’s principle
6. Ionization reaction
a. Strong acids/bases
b. Measuring pH: using
i. indicators
ii. litmus paper, pH paper
iii. formula: pH = - log [H+]
1. pH value: 1 - 7 - 14
acidic (1- <7); neutral (@7) - basic (>7 – 14)
7. Thermochemistry
a. Units of heat: calorie(cal), Kilocalorie(kcal), joule (J) , kilojoules,kJ
i. 1 cal = 4.184 J 1 kcal =1000 cal 1 KJ = 1000 J
ii. Specific heat,c = amount of heat,q
or sp. ht [mass of substance, g] X [change in temp, oC]
c = q or q = cm ΔT
m x ΔT amt of heat = sp ht x mass x change in temp
change in temp = final temp – initial temp
units of [Link] = cal/g – oC or J/g – oC or kcal/kg - oC

APPLICATION:
1. When two opposing chemical reactions occur simultaneously at the same rate i.e as the
reactants form the products, the products react to form back the reactants, the system is at
chemical equilibrium
- They are called reversible reactions
- But not all reactions are reversible
- Equilibrium constant expression, Keq of a reversible reaction:
aA + bB ⇆ cC + dD
where a,b,c,d are coefficients of the balanced equation
 Keq = [ C ]c [ D ]d molarity is represented as [ ]
[ A ] a [ B ]b
ONLY GASEOUS COMPONENTS IN THE MIXTURE ARE INCLUDED IN THE EQUILIBRIUM
EXPRESSION ; equations should always be a BALANCED equation

Example: (1) 2 HI (g) ⇆ H2 (g) + I2 (g)

Equilibrium constant expression, Keq = [ H2 ] [ I2]
[ HI ]2

( 2) 2 NO2(g) + 7 H2 (g) ⇆ 2 NH3 (g) + 4 H2O (g)

Keq = [ NH3 ] 2 [ H2O ] 4

[ NO2 ] 2 [ H2 ] 7

(3) NH4Cl(s) ⇆ NH3 (g) + HCl (g)

COMPUTING the value, Kc from the Keq if amounts of reactants or products at equilibrium is known:

Equilibrium constant, Kc determination

At a temperature of 350 oC, the equilibrium concentration for the reaction

N2 (g) + 3 H2 (g) ⇆ 2 NH3 (g)
are: [ N2 ] = 0.885M [ H2 ] = 0.665M [ NH3 ] = 1.230 M

Keq = [ NH3 ] 2
[ N2 ] [ H2 ] 3

Substituting the concentrations of each GASEOUS component, equilibrium constant, Kc is:

Kc = [ 1.230 M ] 2 = 5.81 / M2
[ 0.885M ] [ 0.665M ]3

2. LE CHATELIER’S PRINCIPLE
(A) Effect of changing concentrations: Adding or removing a reactant or product from a reaction
mixture at equilibrium will always upset the equilibrium.
Example: N2 (g) + 3 H2 (g) ⇆ 2 NH3 (g)

Suppose some additional H2 or N2 is added to the equilibrium mixture. The equilibrium will shift
to the right i.e FORWARD REACTION rate will increase in order to use up the additional H 2 or N2.
In addition the H2 or N2 concentration will have decreased (some N2 will react with the H2) and
the NH3 concentration will increase since it is what forms when N 2 and H2 reacts.

Also if some NH3 (g) are removed from the system, FORWARD REACTION will be favored
meaning the remaining N2 or H2 will react to supply the removed NH3.
 Suppose additional NH3 (g) is added to the mixture, the reaction shifts to the LEFT i.e
BACKWARD REACTION so the amount of N2 and H2 will increase until equilibrium state will be
attained after the NH3 amount added is used up to produce more N2 or H2

(B) Effect of change in temperature: Raising the temperature of the equilibrium mixture
causes the equilibrium condition to shift in the direction of the ENDOTHERMIC REACTION.
Lowering the temperature causes a shift in the direction of EXOTHERMIC REACTION

The forward reaction or backward reaction should first be identified whether it is

ENDOTHERMIC or EXOTHERMIC REACTION before the change in the direction is known

Example: (1) Is the conversion of SO2 (g) from SO3 (g) favored at high or low temperature?

2 SO2 (g) + O2 (g) ⇆ 2 SO3 (g) ΔH = - 180 KJ/mol

ΔH = enthalpy; expresses the amount of heat or heat content of the system

If ΔH is negative HEAT IS LOST in the formation of the product (forward reaction)
therefore the forward reaction is an EXOTHERMIC reaction
If ΔH is positive HEAT IS GAINED in the formation of the product therefore the forward
reaction is an ENDOTHERMIC REACTION

Answer: in the reaction, the formation of SO3 (forward reaction) is exothermic since ΔH is
negative and so the backward reaction will be an endothermic reaction.
The conversion of SO2 from SO3 will follow the backward reaction which is an endothermic
reaction and meaning a lower temperature.

(2) Given the reaction: 2 POCl3 (g) ⇆ 2 PCl3 (g) + O2 (g) ΔH = 508 KJ
or Heat + 2 POCl3(g) ⇆ 2 PCl3 (g) + O2(g)

What will be the shift in the direction of reaction if reaction is (a)heated; (b)cooled

ANSWER: Since the forward reaction is endothermic (heat is needed since it is placed as a
reactant; AH= + ) and the backward reaction is an exothermic reaction ( direction of
reactions cannot be both endothermic or both exothermic)

a) If heated or raising temperature: endothermic direction = FORWARD DIRECTION or to

the RIGHT
b) If cooled: exothermic direction = BACKWARD DIRECTION or to the LEFT

( C) Effect of change in pressure – Pressure changes affect systems at equilibrium only when GASES are
involved or only where the chemical reaction changes in the total number of moles in the gaseous state
occurs.
According to Le Chatelier’s principle, the stress of increased pressure is relieved by decreasing the
number of moles of gaseous substances which is accomplished by shifting the direction of reaction
towards the FEWER number of moles

Decreasing the pressure will shift the direction of reaction towards the GREATER number of moles
Total moles of reactants and total moles of products are considered in determining the shifting of the
direction of reaction

Example: Consider the reaction: 2 NO2(g) + 7 H2 (g) ⇆ 2 NH3 (g) + 4 H2O (g)

What direction of reaction will be favored if there is (a) an increase in pressure; (b) a decrease in
pressure?

Answer: Total moles of reactants : 2 moles NO2 + 7 moles H2 = 9 moles

Total moles of products: 2 moles NH3 + 4 moles H2O = 6 moles

(a) Increase in pressure: towards fewer number of moles i.e 6 moles ; towards the product side,
FORWARD direction or RIGHT side
(b) Decrease in pressure: towards the greater number of moles i.e 9 moles; towards the reactants
side; BACKWARD direction or LEFT side

3. IONIC EQUILIBRIUM

Ionization – formation of ions out of a solution (aqueous solution); ions form only when in
solution (like salts, acids, bases)
Example: NaCl (aq) → Na+ + Cl-
HCl (aq) → H+ + Cl- (strong acids ionize completely)
NaOH (aq) → Na+ + OH - (strong base ionize completely)
- Weak acids (ex. HC2H3O2) and weak bases (ex. NH4OH) are partially ionized, some are ionic &
others are still molecular in size when in aqueous solution

Ways to measure acidity/basicity : use pH

pH = -log [H+] pH range; 1 - 7 - 14 ; if pH= 1 to less than 7 are acidic ; if pH = exactly 7 then
it is neutral; if pH = greater than 7 until 14 the it is basic
pH is the hydrogen ion (H+) potential of a solution

APPLICATION:
Calculate the pH of the following and the two dilute solutions of each as described:
(a) 5 mL of the original solution is measured and added to water to make a final volume of
250 mL.
(b) 5 mL of the solution in (a) is diluted again using water to a total volume of 500mL
1) 0.0063M HCl 2) 0.050M NaOH
Strong acids and bases have complete ionization; whatever is the concentration of the
solution (its source), it is also the concentration of the ions produced; it is 100% ionized
HCl (aq) → H+ + Cl-
0.0063M 0.0063M 0.0063M

pH = - log [ H +]
= - log [ 0.0063 ]
= - ( - 2.2006590 = 2.2
 a) Dilute solution #1 V1C1 = V2 C2
(5 mL)(0.0063M) = (250mL)(C2)
C2 = (5 mL)(0.0063M) = 1.26 x 10-4 M HCl diluted solution
250mL
pH = - log 1.26x10-4
= - ( - 3.8996) = 3.90
b) Dilute solution #2
HCl (aq) → H+ + Cl-
1.26x10-4M 1.26 x 10-4 M 1.26 x 10-4M
V1C1 = V2C2
(5 mL)(1.26 x 10-4M) = (500mL)(C2)
C2 = (5mL)(1.26x10-4M)
500mL
= 1.26x10-6M
pH = - log (1.26x10-6)
= - (-5.8996) = 5.90
CONCLUSION:
As the concentration is decreased (like by frequent dilution) the acidity decreases
towards being neutral @pH=7.

2) 0.050M NaOH solution

NaOH(aq) → Na+ + OH- since it is a strong base
0.050M 0.050M 0.050M
-even if it is a strong base but added to water, HOH ( has H+ and OH-) therefore there is still the
presence of H+ and since its OH- concentration from NaOH is known, pOH is rather computed first
before the pH can be further determined using another formula: pH + pOH = 14 (pH &pOH in an
aqueous solution is equal to 14)
pOH = - log [OH-]

pOH = - log[0.050] pH = 14 - pOH

= - [-1.30] = 14 – 1.30
= 1.30 (extremely basic) = 12.7 ( it is basic; pH is above 7)
a) Dilute solution #1 V1C1 = V2C2 similar to 0.0063M HCl diluted twice using same amounts)
(5 mL)(0.050M) = (250mL) C2
C2 = (5mL)(0.050M) = 1.00x10-3 M refers to [OH-] of NaOH diluted solution #1
250mL
Since NaOH is a strong base, [OH-] is the same as the diluted solution #1

pOH = - log [OH-] pH = 14 - pOH

= - log[ 1.0x10-3] = 14 – 3
= - (-3) = 11
= 3
b) Dilute solution #2 V1C1 = V2C2
(5mL)( 1.00 x 10-3M) = (500mL)( C2 )
C2 = (5mL)(1.00x10-3M) = 1.00x10-5M refers to [OH-] of NaOH diluted #2
500mL
pOH = - log [OH-] pH = 14 - pOH
= - log [ 1.00x10-5] = 14 - 5
 = - ( -5) =5 = 9
CONCLUSION: As the concentration is decreased (like by frequent dilution) the basicity decreases
towards being neutral @pH=7.
4. THERMOCHEMISTRY
APPLICATION: Units of heat/specific heat problem solving
A) Conversion of units:
a. How many (1) joules , (2) calories and (3) kcal are there in 43.5 KJ
Answer: Since 1 cal = 4.184J , 1 kcal = 1000cal, 1 KJ = 1000 J

(1) ? J = 43.5 KJ x 1000 J = 4.35 x 104 J

1 KJ
(2) ?cal = 43.5 x 104 J x 1 cal = 10396.7495 cal = 1.04 x 104 cal
4.184 J

(3) ?kcal= 10396.7495 cal x 1 kcal = 10.3967495 kcal = 10.4 kcal

1000 cal
Another way of computing still using dimensional analysis:

? kcal = 43.5 KJ x 1000 J x 1 cal x 1 kcal = 10.3967495 kcal = 10.4 kcal

1 KJ 4.184 J 1000 cal

B) Specific heat, c = amount of heat, q

mass of substance,g x change in temp, oC
Change in temp = final temp, Tf – initial temp,Ti
1. When 75.4g sample of nickel loses 1.43 KJ , its temperature falls from 88.5oC to 45.8oC.
What is the specific heat of nickel in KJ/g-oC?

Computation: given: mass of nickel = 75.4 g

Amount of heat loss = 1.43 KJ (since heat is lost, q is negative in sign
Tf = 45.8oC Ti = 88.5oC
Formula: sp ht = amount of heat
mass x (Tf – Ti)
sp. Ht = - 1.43 KJ = - 1.43 KJ = 4.44 x 10-4 KJ/g-oC
o o o
(75.4g)(45.8 C – 88.5 C) - 3219.58 g- C
2. 6.28 KJ is applied to a sample of water and the temperature rises from 22.3 oC to
28.9oC. What is the mass of the water sample?
(specific heat of water: 1 cal/g-oC or 4.184 J/g-oC)
Computation: Given: amount of heat = 6.28 KJ ?J = 6.28KJ x 1000 J = 6.28x10 3 J
Tf = 28.9oC Ti = 22.3oC 1 KJ
sp ht = amount of heat
mass x (Tf – Ti)
4.184 J = 6.28x103 J
o
g- C (mass)( 28.9oC – 22.3oC)
mass = 6.28x103 J = 227.4176 g = 227 g water
o o o
(4.184 J/g- C)( 28.9 C – 22.3 C)

3. if sp ht, c = q ΔT = Tf - Ti
Mass x ΔT
 Then q = sp ht x mass x ΔT or q = c x m x ΔT
Also applying the Law of conservation of energy: heat loss of a warmer substance is
equal to heat gained by a colder substance. Heat is conserved.
Heat loss by warmer substance i.e. - q = heat gained colder substance i.e. + q

-q = + q then since q = c x m x ΔT

-(c x m x ΔT) = (c x m x ΔT)

APPLICATION:
A 20.0 g piece of metal at 203oC is dropped into 100.0g water at 25.0oC. The water
temperature rises to 29.0oC. Calculate the specific heat of the metal in J/g-oC .(assuming
that all heat loss by the metal is absorbed by the water)
COMPUTATION: Given: metal: mass = 20.0g Ti = 203 oC Tf for both metal & water = 29.0oC
water: mass = 100.0 g Ti = 25.0oC
heat loss by metal (warmer since Ti is higher) = heat gained by water (colder since Ti is lower)
-q metal = +q water
-(c x m x ΔT) of metal = (c x m x ΔT) of water
-( c )(20.0g)( 29.0oC – 203oC) = ( 4.184 J/g-oC)(100.0g)(29.0oC – 25.0oC)
- (c) (20.0g)( - 174oC) = 1673.6 J
- (c) (-3480) g-oC = 1673.6 J
(sp ht) (3480 g-oC ) = 1673.6 J
Sp ht or c = 1673.6 J = 0.48092 J/g-oC = 0.481 J/g-oC
o
3480 g- C

ASSIGNMENT: Considered as big task. Always work on a BALANCED equation.

I. Given the following chemical equations, (a) BALANCE the equation, (b) write the chemical
equilibrium expression, Keq
1. NO (g) + O2 (g) ⇆ NO3 (g)
2. CS2 (g) + H2(g) ⇆ CH4 (g) + H2S (g)
3. NH3 (g) + O2(g) ⇆ NO(g) + H2O(g)
4. NOCl(g) ⇆ NO (g) + Cl2(g)
5. Na2CO3 (s) + C(s) + N2(g) ⇆ NaCN(s) + CO (g)
II. What is the equilibrium expression, keq and equilibrium constant, Kc of the given equation?
N2(g) + O2(g) ⇆ NO2(g)
If the equilibrium concentrations are: [N2] = 0.0013M ; [O2] = 0.0024M; [NO2]=0.00065M

III. Given the following equilibrium mixture of gases at 500 oC where the ΔH is negative,
CO(g) + O2(g) ⇆ CO2 (g) (unbalanced)
STATE the direction in which the equilibrium would be shifted upon the application of the
following changes. (answer either: BACKWARD direction or FORWARD direction)
1. Adding more O2 at constant temperature
2. Increasing the temperature
3. Cooling below 100oC
4. Adding a catalyst
5. Double the pressure
 IV. For the reaction: C6H6(g) + H2(g) ⇆ C6H12(g) ΔH is positive
Determine the direction that the equilibrium will be shifted by the following changes:
1. Decreasing the concentration of C6H12 (g)
2. Increasing the concentration of H2(g)
3. Increasing the temperature
4. Decreasing the temperature
5. Increasing the pressure
V. Calculate the initial pH of the following and the two dilute solutions of each as described:
A) 5 mL of the original solution is measured and added to water to make a final volume of 500mL.
B) 5 mL of the solution in (A) is diluted again using water to a total volume of 950mL
1. 4.20x10-3M HNO3 2) 0.0105M KOH

VI. 1) What is 1032 J of heat in (a) KJ (b) calories (c) kcal

2) When a piece of graphite weighing 3.00g absorbs 62.8 J, the temperature changes from 25.0oC to
54.0oC. What is the specific heat of graphite?
3) A 500.0 g piece of iron is heated in a flame to a temperature of 656 oC and dropped into 400.0g
water at 10.0oC. The temperature of the water rose to a final temperature of 90.0oC. What is the
specific heat of iron in J/g-oC