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Prepared by Lawrence Kok
Tutorial on Dynamic Equilibrium, Homogeneous, Heterogeneous Equilibrium and Equilibrium Constant.
Chemical Reaction
ReversibleIrreversible
A C
• Open system• Limiting reactants used up.• Reaction stop• Ea low, energetic/kinetic favourable -ΔH
C
A C
• Closed system (No matter escapes)• Forward rxn – products • Reverse rxn - reactants• Product dissociate form reactant
C
Reaction going onReaction stop
Open system Unidirection
A
C
Closed system - No matter escape Both direction - equilibrium
A
CConc remain constantVs
A A
Dynamic Equilibrium
Chemical Reaction
ReversibleIrreversible
A C
• Open system• Limiting reactants used up.• Reaction stop• Ea low, energetic/kinetic favourable -ΔH
C
A C
• Closed system (No matter escapes)• Forward rxn – products • Reverse rxn - reactants• Product dissociate form reactant
C
Reaction going onReaction stop
Open system Unidirection
A
C
Closed system - No matter escape Both direction - equilibrium
A
C
• Both forward and reverse rxn continue at equilibrium• Movement of particles bet both sides goes on• Conc of reactants and products remain constant Rate of forward = Rate of reverse• Formation and decomposition continues• Two/more opposing rxn take place same time, same rate
At dynamic equilibrium
Conc remain constantVs
A A
Photo: http://declanfleming.com/man-vs-escalator-equilibrium-model/
http://chemistry.tutorvista.com/physical-chemistry/reversible-reaction-and-irreversibility.html
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
Liquid -Vapour equilibrium Br2(l) ↔ Br2(g)
initial equilibrium
• Liq and gas Br2 in dynamic equilibrium• Add more liq Br2 will increase its liq mass but not conc• Dynamic equilibrium, Kc bet liq and gas Br2 remain the same• Macroscopic level – colour/intensity liq/gas Br2 remain constant• Microscopic level – liq/gas Br2 equilibrium, forward/ reverse rxn going
on (Rate of Vapourization = Rate of Condensation)
Br2 (l) Br2(g)
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
Liquid -Vapour equilibrium Br2(l) ↔ Br2(g)
initial equilibrium
• Liq and gas Br2 in dynamic equilibrium• Add more liq Br2 will increase its liq mass but not conc• Dynamic equilibrium, Kc bet liq and gas Br2 remain the same• Macroscopic level – colour/intensity liq/gas Br2 remain constant• Microscopic level – liq/gas Br2 equilibrium, forward/ reverse rxn going
on (Rate of Vapourization = Rate of Condensation)
NO change in conc liquid/vapour
Rate of evaporation = Rate of condensation
Rate of evaporation > Rate of condensation
More vapour form
Rate condensation increase
Initially
Br2 (l) Br2(g)
time
Rate
Rate of condensation
Rate of evaporation
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
Liquid -Vapour equilibrium Br2(l) ↔ Br2(g)
initial equilibrium
• Liq and gas Br2 in dynamic equilibrium• Add more liq Br2 will increase its liq mass but not conc• Dynamic equilibrium, Kc bet liq and gas Br2 remain the same• Macroscopic level – colour/intensity liq/gas Br2 remain constant• Microscopic level – liq/gas Br2 equilibrium, forward/ reverse rxn going
on (Rate of Vapourization = Rate of Condensation)
NO change in conc liquid/vapour
Rate of evaporation = Rate of condensation
Rate of evaporation > Rate of condensation
More vapour form
Rate condensation increase
Initially
Br2 (l) Br2(g)
time
Rate
Rate of condensation
Rate of evaporation
Why add more liq Br2 will not change intensity
vapour?
Remove Br2 gas - Conc Br2 gas change - affect Kc (Rate of Vapourization > Rate of Condensation)
Density = Mass Vol
Conc = Mass VolMore mass - more vol
Density/conc still same
Rate of vapourization/condensation depend on change in conc Br2
(Rate of Vapourization = Rate of Condensation) No change in conc/intensity vapour Br2
Add more Br2
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
Solute-solution equilibrium Sugar(s) ↔ Sugar (aq)
• Sugar crystals/solution in dynamic equilibrium• Add sugar will not increase sugar conc/sweetness (saturated sol)• Dynamic equilibrium, Kc bet sugar solid and sol remain same• Macroscopic level – conc/sweetness remain constant• Microscopic level – crystal/sol in equilibrium, forward/reverse rxn going on (Rate of Dissolving = Rate of Crystallization)
Sugar (s) Sugar (aq)
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
NO change in conc sugar sol
Rate of dissolving = Rate of crystallization
Rate of dissolving > Rate of crystallization
More sugar dissolve - saturated sol form
Rate crystallization increase
Initially
time
Rate
Rate of crystallization
Rate of dissolving
Solute-solution equilibrium Sugar(s) ↔ Sugar (aq)
• Sugar crystals/solution in dynamic equilibrium• Add sugar will not increase sugar conc/sweetness (saturated sol)• Dynamic equilibrium, Kc bet sugar solid and sol remain same• Macroscopic level – conc/sweetness remain constant• Microscopic level – crystal/sol in equilibrium, forward/reverse rxn going on (Rate of Dissolving = Rate of Crystallization)
Sugar (s) Sugar (aq)
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
NO change in conc sugar sol
Rate of dissolving = Rate of crystallization
Rate of dissolving > Rate of crystallization
More sugar dissolve - saturated sol form
Rate crystallization increase
Initially
time
Rate
Rate of crystallization
Rate of dissolving
Why add more sugar will not change
sweetness/conc?
Solute-solution equilibrium Sugar(s) ↔ Sugar (aq)
• Sugar crystals/solution in dynamic equilibrium• Add sugar will not increase sugar conc/sweetness (saturated sol)• Dynamic equilibrium, Kc bet sugar solid and sol remain same• Macroscopic level – conc/sweetness remain constant• Microscopic level – crystal/sol in equilibrium, forward/reverse rxn going on (Rate of Dissolving = Rate of Crystallization)
Adding more water – affect Kc – Conc sugar changes ( Rate of Dissolving > Rate of Crystallization )
Sugar (s) Sugar (aq)
Add more sugar
More mass - more volDensity/conc still same
Conc = Mass Vol
Density = Mass Vol
Rate of dissolving/crystallization depend on change in sugar conc
(Rate of Dissolving = Rate of Crystallization) No change in sugar conc (solution)
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
Solid-vapour equilibrium Iodine(s) ↔ Vapour(g)
• I2 solid/vapour in dynamic equilibrium• Add more I2 will not increase vapour pressure I2 • Equilibrium, Kc bet solid/vapour remain the same (Temp dependent)• Macroscopic level – Vapour pressure/intensity remain constant• Microscopic level – solid/vapour in equilibrium, forward/reverse rxn going
on (Rate of Vapourization = Rate of Crystallization)
Iodine (s) Iodine (g)
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
NO change in conc vapour
Rate of vapourization = Rate of crystallization
Rate of vapourization > Rate of crystallization
More iodine sublime
Rate crystallization increase
Initially
time
Rate
Rate of crystallization
Rate of vapourization
Solid-vapour equilibrium Iodine(s) ↔ Vapour(g)
• I2 solid/vapour in dynamic equilibrium• Add more I2 will not increase vapour pressure I2 • Equilibrium, Kc bet solid/vapour remain the same (Temp dependent)• Macroscopic level – Vapour pressure/intensity remain constant• Microscopic level – solid/vapour in equilibrium, forward/reverse rxn going
on (Rate of Vapourization = Rate of Crystallization)
Iodine (s) Iodine (g)
Vapour pressure same
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
initial equilibrium
NO change in conc vapour
Rate of vapourization = Rate of crystallization
Rate of vapourization > Rate of crystallization
More iodine sublime
Rate crystallization increase
Initially
time
Rate
Rate of crystallization
Rate of vapourization
Why add more I2 will not change vapour
pressure/intensity?
Solid-vapour equilibrium Iodine(s) ↔ Vapour(g)
• I2 solid/vapour in dynamic equilibrium• Add more I2 will not increase vapour pressure I2 • Equilibrium, Kc bet solid/vapour remain the same (Temp dependent)• Macroscopic level – Vapour pressure/intensity remain constant• Microscopic level – solid/vapour in equilibrium, forward/reverse rxn going
on (Rate of Vapourization = Rate of Crystallization)
Using a bigger container. Will vapour pressure change?
Iodine (s) Iodine (g)
Add more I2
More mass - more vol Density/conc still same
Conc = Mass Vol
Density = Mass Vol
Rate of vapourization/crystallization depend on change in conc I2 (Temp dependent)
(Rate of Vapourization = Rate of Crystallization)
Vapour pressure same
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
Liquid -Vapour equilibrium Br2(l) ↔ Br2(g)
initial equilibrium
2NO2(g) N2O4(g)
combining decomposition
brown colourless
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
Liquid -Vapour equilibrium Br2(l) ↔ Br2(g)
initial equilibrium
NO change in conc liquid/intensity vapour/vapour pressure
Rate of evaporation = Rate of condensation
Liquid Br2 evaporate
Macroscopic – no changes
2NO2(g) N2O4(g)
Physical system Chemical system
Vapour Br2 condense Forward rate rxnRate Combining
Backward rate rxnRate decomposition
Reversible rxn happening, same time with same rate
Rate of forward = Rate of backward
Conc of reactants and products remain UNCHANGED not EQUAL
combining decomposition
brown colourless
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
2NO2(g) N2O4(g)
combining dissociation
Conc vs time Rate vs timeConc
Time
Conc NO2
Conc N2O4
Dynamic Equilibrium
Closed system
Reversible
Forward Rate, Kf
Reverse Rate, Kr
2NO2(g) N2O4(g)
Chemical system
Forward rate rxnRate Combining
Backward rate rxnRate dissociation
Reversible rxn happening, same time with same rate
Rate of forward = Rate of backward
Conc of reactant and productremain UNCHANGED/CONSTANT not EQUAL
combining dissociation
Conc vs time Rate vs timeConc
Time
Conc NO2
Conc N2O4
With time• Conc NO2 decrease ↓ - Forward rate decrease ↓
• Conc N2O4 increase ↑ - Backward rate increase ↑
2NO2(g) N2O4(g)Forward rate
Backward rate
Forward Rate = Backward Rate
Conc NO2 and N2O4 remain UNCHANGED/CONSTANT
brown colourless
How dynamic equilibrium is achieved in closed system?
Conc of NO2 decrease ↓over time
NO2
2NO2(g) N2O4(g)
Conc of N2O4 increase ↑ over time
N2O4
1 As reaction proceeds concentration
How dynamic equilibrium is achieved in closed system?
Conc of NO2 decrease ↓over time
Forward rate, Kf decrease ↓ over time
NO2
2NO2(g) N2O4(g)
Conc of N2O4 increase ↑ over time
N2O4
Reverse rate, Kr increase ↑ over time
NO2
N2O4
1
2
As reaction proceeds concentration
As reaction proceeds rate
How dynamic equilibrium is achieved in closed system?
Conc of NO2 decrease ↓over time
Forward rate, Kf decrease ↓ over time
Forward Rate = Reverse Rate
NO2
2NO2(g) N2O4(g)
Conc of N2O4 increase ↑ over time
N2O4
Reverse rate, Kr increase ↑ over time
NO2
N2O4
1
2
Conc of reactant/product remain constant
Rate
3
Time
Conc
NO2
N2O4
At dynamic equilibrium
As reaction proceeds concentration
As reaction proceeds rate
Time
Dynamic Equilibrium
Reversible (closed system)
Forward Rate, K1 Reverse Rate, K-1
Conc of product and reactant at equilibrium
At Equilibrium
Forward rate = Backward rateConc reactants and products remain CONSTANT/UNCHANGE
aA(aq) + bB(aq) cC(aq) + dD(aq)
coefficient
Solid/liq not included in Kc
Conc represented by [ ]
K1
K-1
Equilibrium Constant Kc
Conc vs time Rate vs time
A + B
C + D
Conc
Time
Dynamic Equilibrium
Reversible (closed system)
Forward Rate, K1 Reverse Rate, K-1
Kc = ratio of molar conc of product (raised to power of their respective stoichiometry coefficient) to molar conc of reactant (raised to power of their respective stoichiometry coefficient)
Conc of product and reactant at equilibrium
At Equilibrium
Forward rate = Backward rateConc reactants and products remain CONSTANT/UNCHANGE
Equilibrium Constant Kc
aA(aq) + bB(aq) cC(aq) + dD(aq)
coefficient
Solid/liq not included in Kc
Conc represented by [ ]
K1
K-1
ba
dc
cBA
DCK
1
1
K
KKc
Equilibrium Constant Kc
express in
Conc vs time Rate vs time
A + B
C + D
Conc
Time
Click here notes on dynamic equilibrium
Excellent Notes
K1 = forward rate constant
K-1 = reverse rate constant
Magnitude of Kc
ba
dc
cBA
DCK
Extend of reaction
How far rxn shift to right or left?
Not how fast
ba
dc
cBA
DCK
cKcK
Position of equilibrium
1
Large Kc
• Position equilibrium shift to right• More product > reactant
Magnitude of Kc
ba
dc
cBA
DCK
Extend of reaction
How far rxn shift to right or left?
Not how fast
ba
dc
cBA
DCK
Small Kc
• Position equilibrium shift to left• More reactant > product
cKcK
Position of equilibrium
2CO2(g) ↔ 2CO(g) + O2(g)
92103 cK
2H2(g) + O2(g) ↔ 2H2O(g)
81103cK
H2(g) + I2(g) ↔ 2HI(g)
2107.8 cK1
Moderate Kc
• Position equilibrium lies slightly right• Reactant and product equal amount
Reaction completion
Large Kc
• Position equilibrium shift to right• More product > reactant
Magnitude of Kc
ba
dc
cBA
DCK
Extend of reaction
How far rxn shift to right or left?
Not how fast
ba
dc
cBA
DCK
Small Kc
• Position equilibrium shift to left• More reactant > product
cKcK
Position of equilibrium
2CO2(g) ↔ 2CO(g) + O2(g)
92103 cK
2H2(g) + O2(g) ↔ 2H2O(g)
81103cK
H2(g) + I2(g) ↔ 2HI(g)
2107.8 cK1
Moderate Kc
• Position equilibrium lies slightly right• Reactant and product equal amount
Reaction completion
Product favouredReactant favoured Reactant/Product equal
cKTemp
dependentExtend of rxn
Not how fast
Equilibrium Constant Kc
ba
dc
cBA
DCK
aA(aq) + bB(aq) cC(aq) + dD(aq)
Conc of product and reactant at equilibrium
Equilibrium expression HOMOGENEOUS gaseous rxn
4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g) N2(g) + 3H2(g) ↔ 2NH3(g)
NH4CI(s) ↔ NH3(g) + HCI(g)
2SO2(g) + O2(g) ↔ 2SO3(g)
Equilibrium expression HETEROGENOUS rxn
CaCO3(s) ↔ CaO(g) + CO2(g)
CH3COOH(l) + C2H5OH(l) ↔ CH3COOC2H5(l) + H2O(l)
Equilibrium expression HOMOGENEOUS liquid rxn
Cu2+(aq) + 4NH3(aq) ↔ [Cu(NH3)4]2+
Reactant/product same phase
Reactant/product diff phaseSolid and liq - conc no change (not included)
Equilibrium Constant Kc
ba
dc
cBA
DCK
aA(aq) + bB(aq) cC(aq) + dD(aq)
Conc of product and reactant at equilibrium
Equilibrium expression HOMOGENEOUS gaseous rxn
4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g) N2(g) + 3H2(g) ↔ 2NH3(g)
NH4CI(s) ↔ NH3(g) + HCI(g)
2SO2(g) + O2(g) ↔ 2SO3(g)
524
3
62
4
ONH
OHNOKc
321
2
23
HN
NHKc
113 HCINHKc
04
113
CINH
HCINHKc
122
2
23
OSO
SOKc
Equilibrium expression HETEROGENOUS rxn
CaCO3(s) ↔ CaO(g) + CO2(g)
03
12
1
CaCO
COCaOK c
121 COCaOK c
CH3COOH(l) + C2H5OH(l) ↔ CH3COOC2H5(l) + H2O(l)
152
13
12
1523
OHHCCOOHCH
OHHCOOCCHK c
Equilibrium expression HOMOGENEOUS liquid rxn
Cu2+(aq) + 4NH3(aq) ↔ [Cu(NH3)4]2+
43
12
243 )(
NHCu
NHCuK c
Reactant/product same phase
Reactant/product diff phaseSolid and liq - conc no change (not included)
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
Rate vs Time
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
20 20
Rate forward = ½ breakdown = ½ x 20 = 10
Rate reverse = ¼ form = ¼ x 20 = 5
Rate vs Time
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
20 20
Rate forward = ½ breakdown = ½ x 20 = 10
Rate reverse = ¼ form = ¼ x 20 = 5
15 25
Rate forward = ½ breakdown = ½ x 15 = 8
Rate reverse = ¼ form = ¼ x 25 = 6
Rate vs Time
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
20 20
Rate forward = ½ breakdown = ½ x 20 = 10
Rate reverse = ¼ form = ¼ x 20 = 5
15 25
Rate forward = ½ breakdown = ½ x 15 = 8
Rate reverse = ¼ form = ¼ x 25 = 6
13 27
Rate forward = ½ breakdown = ½ x 13 = 7
Rate reverse = ¼ form = ¼ x 27 = 7
Rate vs Time
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
20 20
Rate forward = ½ breakdown = ½ x 20 = 10
Rate reverse = ¼ form = ¼ x 20 = 5
15 25
Rate forward = ½ breakdown = ½ x 15 = 8
Rate reverse = ¼ form = ¼ x 25 = 6
13 27
Rate forward = ½ breakdown = ½ x 13 = 7
Rate reverse = ¼ form = ¼ x 27 = 7
13 27
At dynamic Equilibrium Rate forward = Rate reverseBreakdown (7) = Formation (7)
At dynamic Equilibrium Conc reactant 13 /Product 27 constant
Rate vs Time
Conc vs Time
How dynamic equilibrium is achieved in a closed system?
40 0
Rate forward = ½ breakdown = ½ x 40 = 20
Rate reverse = ¼ form = ¼ x 0 = 0
20 20
Rate forward = ½ breakdown = ½ x 20 = 10
Rate reverse = ¼ form = ¼ x 20 = 5
15 25
Rate forward = ½ breakdown = ½ x 15 = 8
Rate reverse = ¼ form = ¼ x 25 = 6
13 27
Rate forward = ½ breakdown = ½ x 13 = 7
Rate reverse = ¼ form = ¼ x 27 = 7
13 27
At dynamic Equilibrium Rate forward = Rate reverseBreakdown (7) = Formation (7)
At dynamic Equilibrium Conc reactant 13 /Product 27 constant
Rate vs Time
4/1
2/1
..tan..
..tan..
1
1 reversetconsrate
forwardtconsrate
K
K
213
27
tan
treac
productK c 2
4/1
2/1
1
1 K
KK cor
Click here to view simulationClick here simulation using paper clips Click here simulation on reversible rxn
Click here on reversible rxn
Simulation on Dynamic equilibrium
Click here on equilibrium constant