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CHAPTER 6

CHEMICAL EQUILIBRIUM

6.3 Le Chatelier’s Principle

1
Learning Outcomes

At the end of the lesson, students should be able to:


(a) State Le Chatelier’s principle
(b) Apply the Le Chatelier’s principle to explain
the effect of the following factors on a system
at equilibrium:
i) Concentration of reacting species
ii. Pressure by changing volume
iii. Addition of inert gas at constant volume and at
constant pressure
iv. Temperature
v. Catalyst.
2
Le Chatelier’s Principle
LE CHATELIER’S PRINCIPLE
States that … when a chemical system is disturbed, it
reestablished equilibrium by undergoing a net
reaction that reduces the effect of the disturbance.

Net reaction refers to the shift in


the equilibrium position of the
system to either right or left.

Henry Louis Le Châtelier


(1850 – 1936)
French chemist
3
Le Chatelier’s Principle
LE CHATELIER’S PRINCIPLE
N2(g) + 3H2(g) 2NH3(g) a chemical system

Add NH3
Original equilibrium: Q=K
Disturbance:  Add NH3
 [NH3] increase
Q≠K

Reduce Disturbance:  reduce increase of [NH3]

 net reaction proceeds to the left


New equilibrium: Q=K 4
Le Chatelier’s Principle
LE CHATELIER’S PRINCIPLE
New
equilibrium

The disturbance
(addition of NH3)
is reduced,
not eliminated.

5
The Effect of Added Cl2 on PCl3–Cl2–PCl5 System

0.163 0.163 0.637

Original New initial New


equilibrium (just after Cl2 added) equilibrium

[PCl5] 0.600 M 0.600 M 0.637 M


[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M 6
Le Chatelier’s Principle
LE CHATELIER’S PRINCIPLE
Factors that Affect the System at Equilibrium

There are four main factors that affect the equilibrium


position of a system.

Concentration
Pressure and volume
Temperature
Presence of Catalyst

7
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN CONCENTRATION
If the concentration increases, the system reacts to
consume some of it.

PCl3(g) + Cl2(g) PCl5(g) [PCl5]


QC =
[PCl3][Cl2]
add Cl2
Qc < KC ( not at equilibrium !!! )
System will reduce the disturbance (increase of [Cl2]) by :
 proceeding to the right
 Consuming some additional Cl2
 [PCl5] increase
8
 [PCl3] decrease
Original New initial New
equilibrium (just after Cl2 added) equilibrium
[PCl5] 0.600 M 0.600 M 0.637 M
[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M

At the new equilibrium: PCl3(g) + Cl2(g) PCl5(g)

 [PCl5] is higher than its original concentration.


 [Cl2] is higher than its original concentration but lower
than the concentration just after the Cl2 added
(disturbance is reduced but not eliminated).
 [PCl3] is lower than its original concentration because
some reacted with the added Cl2. 9
Original New initial New
equilibrium (just after Cl2 added) equilibrium
[PCl5] 0.600 M 0.600 M 0.637 M
[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M

PCl3(g) + Cl2(g) PCl5(g) [PCl5]


KC =
At the original equilibrium: [PCl3][Cl2]
0.600 = 24.0
KC = At a given temperature,
(0.200)(0.125)
KC does not change with
At the new equilibrium: a change in concentration.
0.637
KC = = 24.0
(0.163)(0.163) 10
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN CONCENTRATION
If the concentration decreases, the system reacts to
produce some of it.
remove PCl3
[PCl5]
QC =
PCl (g) + Cl (g) PCl (g) [PCl3][Cl2]
3 2 5

Qc > KC (not at equilibrium)


System will reduce the disturbance (decrease of [PCl3]) :
 proceeding to the left
 [PCl3] and [Cl2] increase
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 [PCl5] decreases
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN CONCENTRATION
Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts in the Equilibrium


Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
12
Le Chatelier’s Principle
Example 2 : H2 (g) + I2 (g) 2HI (g)

Changes in Concentration Effect to Equilibrium Position


 The system must consume the H2
and produce product.
If H2 (reactant) is added to a  The position of equilibrium will
system. shift to the right in order to
≈ [H2] increase decrease [H2].
  [HI]  and [I2]  & [H2] .
 The position of equilibrium will
If H2 (reactant) is removed to shift to the left in order to
a system. increase [H2].
≈ [H2] decrease
  [HI]  and [I2]  & [H2] .
Le Chatelier’s Principle
Example 2 : H2 (g) + I2 (g) 2HI (g)

Changes in Concentration Effect to Equilibrium Position


 The position of equilibrium will
shift to the left in order to
If HI (product) is added to a decrease [HI].
system.  HI decompose to produce H2
and I2  [H2]  & [I2]  and
[HI] .

14
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN CONCENTRATION
Try this …
To improve air quality and obtain a useful product,
sulphur is often removed from coal and natural gas by
treating the fuel contaminant hydrogen sulphide with
O2 :
2H2S(g) + O2(g) 2S(s) + H2O(g)
What would happen to
Answer :
a) [H2O] if O2 is added? a) increases
b) [H2S] if O2 is added? b) decreases
c) [O2] if H2S is removed? c) Increases
d) [H2S] if sulfur is added? d) unchanged
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Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
 Only involve systems with gaseous components.
 Liquids and solids are nearly incompressible.

Change in pressure can occur in 3 ways :

Changing concentration of a gaseous


component.

Adding inert gas.

Changing the volume of the


reaction vessel.
a cylinder–piston assembly
16
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
PCl3(g) + Cl2(g) PCl5(g)
2 mol gas 1 mol gas
Disturbance : volume decrease
 gas pressure immediately increases.
 Qc ≠ KC (not at equilibrium)
System will reduce the disturbance by …
 Reducing the number of gas molecules
 proceeding to the right
 [PCl3] and [Cl2] decrease
 [PCl5] increases. 17
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
PCl3(g) + Cl2(g) PCl5(g)
2 mol gas 1 mol gas
Disturbance : volume increase
 gas pressure immediately decreases.
 Qc ≠ KC (not at equilibrium)
System will reduce the disturbance by …
 Increasing the number of gas molecules
 proceeding to the left
 [PCl3] and [Cl2] increase.
 [PCl5] decreases. 18
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE

19
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE

Change Shifts in the Equilibrium

Increase pressure Side with smaller mole of gas


Decrease pressure Side with bigger mole of gas

Increase volume Side with bigger mole of gas

Decrease volume Side with smaller mole of gas

20
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
You try this …
What effect does an increase in pressure have on each
of the following systems at equilibrium? The
temperature is kept constant and in each case, the
reactants are in a cylinder fitted with a movable piston.
a) A(s) 2B(s)
b) 2A(l) B(l)
c) A(s) B(g)
d) A(g) B(g)
e) A(g) 2B(g)
21
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Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
You try this … Answer !
a) A(s) 2B(s)
b) 2A(l) B(l)
c) A(s) B(g)
d) A(g) B(g)
e) A(g) 2B(g)

22
22
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
You try this …
Consider the following equilibrium systems:
a) 2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
b) PCl5(g) PCl3(g) + Cl2(g) Answer :
a) Right
d) H2(g) + CO2(g) H2O(g) + CO(g) b) Left
c) No change
d) 2NOCl(g) 2NO(g) + Cl2(g) d) Left

Predict the direction of the net reaction in each case as


a result of increasing the pressure (decreasing volume)
on the system at constant temperature.
23
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
You try this …
How would you adjust the volume of the reaction vessel
in order to maximize product yield in the following
reactions?

a) Fe3O4(s) + 4H2(g) 3Fe(s) + 4H2O(g)


b) 2C(s) + O2(g) 2CO(g)
c) Na2O2(s) 2Na(l) + O2(g) Answer :
a) Decrease
d) C2H2(g) + 2H2(g) C2H6(g) b) Increase
c) No effect24
d) Decrease 24
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas
• The total pressure of an equilibrium system can be
changed without changing its volume by adding an
inert gas.
• However, adding an inert gas has no effect on the
equilibrium position .
• The effect of the addition of an inert gas to the
equilibrium system can be studied based on these two
conditions :
I. At constant pressure
II. At constant volume
25
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Pressure
- The partial pressures for the gases in the system are
lowered.
- The net effect is as though the gases at equilibrium are
subjected to a lower total pressure

- According to Le Chatelier’s principle, addition of a


noble gas favours the direction that increases the
number of moles of gas

26
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Pressure
PCl3(g) + Cl2(g) PCl5(g)
2 mol gas noble gas 1 mol gas
Disturbance : addition of inert gas
 Total gas pressure decreases.
System will reduce the disturbance by …
 increasing the number of gas molecules.
 proceeding to the left – more reactants produced
 [PCl3] and [Cl2] increase.
 [PCl5] decreases.
 Equilibrium favours the reactants. 27
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Pressure
2H2O(g) 2H2(g) + O2(g)
2 mol gas noble gas 3 mol gas
Disturbance : addition of inert gas
 Total gas pressure decreases.
System will reduce the disturbance by …
 increasing the number of gas molecules.
 proceeding to the right – more products produced
 [H2] and [O2] increase.
 [H2O] decreases.
 Equilibrium favours the products. 28
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Pressure
H2(g) + I2(g) 2HI(g)
2 mol gas noble gas 2 mol gas
Disturbance : addition of inert gas
 Total gas pressure decreases.
System will reduce the disturbance by …
 increasing the number of gas molecules ????
 Number of moles of reactants and product are
the same !
 The equilibrium position is not affected.
29
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Volume

• The total number of gaseous molecules increases.

• The total pressure of the equilibrium system increases.

• However, the partial pressures of each of the gases in


the equilibrium system remain unchanged

30
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN PRESSURE
Addition of an Inert Gas at Constant Volume
• From Dalton’s law:

PA = nA (RT/V) PA = partial pressure of


any gas, A
• Adding inert gas at constant volume will not change
any of the quantity on the right side of the above
equation.
• So, PA remains constant.
• Therefore, addition of inert gas at constant volume
has no effect on the equilibrium position and the
composition of the equilibrium mixture. 31
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
The change in temperature alters the value of K.

PCl3(g) + Cl2(g) PCl5(g) ΔH = –111 kJ

The forward reaction is exothermic

PCl3(g) + Cl2(g)  PCl5(g) ΔH = –111 kJ


Exothermic  heat released

PCl5(g)  PCl3(g) + Cl2(g) ΔH = +111 kJ


Endothermic  heat absorbed
32
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
Exothermic reaction : heat released
PCl3(g) + Cl2(g)  PCl5(g) + heat ΔH = –111 kJ

Disturbance:  increase in temperature


 “adds” heat to the system
 exothermic reaction is not favorable

Disturbance:  decrease in temperature


 “removes” heat from the system
 exothermic reaction is favorable
33
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
Endothermic reaction : heat absorbed
PCl5(g) + heat  PCl3(g) + Cl2(g) ΔH = +111 kJ

Disturbance:  increase in temperature


 “adds” heat to the system
 endothermic reaction is favorable

Disturbance:  decrease in temperature


 “removes” heat from the system
 endothermic reaction not favorable
34
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
(exothermic)
PCl3(g) + Cl2(g) PCl5(g) ΔH = –111 kJ
(endothermic)
[PCl5]
KC =
[PCl3][Cl2]
Changes Net reaction Exothermic
temperature increase Left K decreases
temperature decrease Right K increases

Temperature decrease favors an exothermic reaction.


35
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
(endothermic)
SO2(g) S (s) + O2(g) ΔH = 178 kJ
(exothermic)
[O2]
KC =
[SO2]
Changes Net reaction Exothermic
temperature increase right K increases
temperature decrease left K decreases

Temperature increase favors an endothermic reaction.


36
i. Exothermic Reaction
Example : N2 (g) + 3H2 (g) 2NH3 (g) ΔH = -ve

T increase T decrease

• Shift the position of equilibrium • Shift the position of equilibrium


in the direction as to decrease in the direction as to increase
the T. the T.
• So, the position of equilibrium • So, the position of equilibrium
will shift to the left in order to will shift to the right in order to
absorbed the heat supplied. released the heat supplied.

• More NH3 will dissociate • More NH3 will be produced


•  [NH3] , [H2]  & [N2] •  [NH3] , [H2]  & [N2] 

• The value of Kc or Kp decrease • The value of Kc or Kp increase


37
ii. Endothermic Reaction
Example : N2 (g) + O2 (g) 2NO (g) ΔH = +ve

T increase T decrease
• Shift the position of • Shift the position of
equilibrium in the direction as equilibrium in the direction as
to decrease the T. to increase the T.
• So, the position of equilibrium • So, the position of equilibrium
will shift to the right in order to will shift to the left in order to
absorbed the heat supplied. released the heat supplied.

• More NO will be produced • More NO will dissociate


•  [NO] , [N2]  & [O2]  •  [NO]  , [N2]  & [O2] 
• The value of Kc or Kp increase • The value of Kc or Kp decrease
38
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
Try this …
How does an increase in temperature affect the
equilibrium concentration of the underlined substance
and the value of K:
a) CaO(s) + H2O(l) Ca(OH)2(g) ΔH = –82 kJ
b) CaCO3(g) CaO(s) + CO2(g) ΔH = 178 kJ
c) C(s) + 2H2(g) CH4(g) ΔH = –75 kJ
d) N2(g) + O2(g) 2NO(g) ΔH = 181 kJ
e) P4(s) + 10Cl2(g) 4PCl5(g) ΔH –1528 KJ

Answer :
a) [Ca(OH)2] decrease, K decrease b) [CO2] increase, K increase c) [H2] increase, K decrease
d) [N2] decrease, K increase e) [PCl5] decrease, K decrease 39
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
CHANGE IN TEMPERATURE
Try this …
Predict the effect of increasing the temperature
on the amounts of products in the following
reactions:
a) CO(g) + 2H2(g) CH3OH(g) DH = –90.7 kJ
b) C(s) + H2O(g) CO(g) + H2(g) DH = 131 kJ
c) 2NO2(g) 2NO(g) + O2(g) (endothermic)
d) 2C(s) + O2(g) 2CO(g) (exothermic)

Answer :
40
a) Decrease b) Increase c) Increase d) No effect
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
PRESENCE OF CATALYST
A catalyst changes the reaction rate but does not
change the yield of the reaction products.
Therefore, a catalyst does not change the composition
of the equilibrium mixture.
Hence, a catalyst does not change the value of KC.
A catalyst increases reaction rates of both the forward
and the reverse reaction to the same extend.
So, the same equilibrium mixture is obtained faster.
Hence, a catalyst has no effect on the equilibrium
position.
41
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
PRESENCE OF CATALYST
Try this …
In an uncatalyzed reaction
N2O4(g) 2NO2(g)
the pressure of the of the gases at equilibrium are :
PN O = 0.377 atm and PNO = 1.5 atm at 100oC.
2 4 2

What would happen


to these pressures if a
catalyst is added to
the mixture ? uncatalyzed catalyzed
42
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium

Change Shift Equilibrium Change to value of K


Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
43
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
Try this … 1
Consider the following equilibrium process between
dinitrogen tetrafluoride (N2F4) and nitrogen
difluoride (NF2):
N2F4(g) 2NF2(g) ΔH = 38.5 kJ

Predict the change in equilibrium if …

a) the reaction mixture is heated


b) NF2 gas is removed
c) the pressure decrease Answer :
a) K increase, equilibrium shift right
d) inert gas, such as He, C
b) K unchanged, equilibrium shift right
C
c) K unchanged, equilibrium shift right
is added C
d) K unchanged, equilibrium unchanged
C
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
Try this … 2

Consider the equilibrium between molecular oxygen


and ozone

3O2(g) 2O3(g) ΔH = 284kJ

What would be the effect of …


a) increasing pressure by decreasing volume
b) increasing pressure by adding O2
c) decreasing the temperature Answer :
a) Right
d) adding a catalyst b) Right
c) Left
d) No change
Le Chatelier’s Principle
Factors that Affect the System at Equilibrium
Try this … 3

Sodium bicarbonate undergoes thermal decomposition


according to the following reaction :
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
How does the equilibrium position shift as a results of
each of the following disturbances : Answer :
a) No change
a) 0.20 atm of argon gas is added b) No change
c) shift to the left
b) NaHCO3(s) is added d) shift to the left
c) Mg(ClO4) is added as a drying agent.
d) Dry ice is added at constant temperature
46
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS
An industrial process for the manufacture of ammonia.

Fritz Haber, a German chemist, who


received the Nobel Prize in
Chemistry in 1918 for his development
for synthesizing ammonia, important
for fertilizers and explosives.

Fritz Haber
1868 - 1934
47
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS
An industrial process for the manufacture of ammonia.

• Nitrogen can be found in many essential natural and


synthetic compounds
• Richest source of nitrogen is the atmosphere - (4 of
every 5 molecules are N2)
• However, due to the low reactivity of N2, the supply of
usable nitrogen has become limited.
• Due to the strong triple bond that holds the two N
atoms together, nitrogen atom is very difficult to “fix”
(combine) with other atoms.
48
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS
Nearly 13% of nitrogen fixation on earth is accomplished
industrially through the Haber process for the formation
of ammonia from its elements :

N2(s) + 3H2(g) 2NH3(g) ΔH = –91.8 kJ

Three ways to maximize the yield of ammonia :

 Decrease [NH3]
 Decrease volume (increase pressure)
 Decrease temperature
49
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS

N2(s) + 3H2(g) 2NH3(g) ΔH = –91.8 kJ

Decrease [NH3]
• Product : Ammonia
• By removing ammonia, the system will produce
more in continual drive to re-attain equilibrium
• The equilibrium will shift to the right to produce
more ammonia (product).
50
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS

N2(s) + 3H2(g) 2NH3(g) ΔH = –91.8 kJ


4 mol of gas 2 mol of gas

Decrease the volume (increase pressure)


• 4 mol of gas reacts to form 2 mol of gas.
• Decreasing the volume will shift the equilibrium
towards fewer moles of gas.
• The equilibrium will shift to the right to produce
more ammonia (product).
51
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS

N2(s) + 3H2(g) 2NH3(g) ΔH = –91.8 kJ

Decrease the temperature


• Formation of ammonia is an exothermic process.
• Decreasing temperature (removing heat) will shift
the equilibrium to the right to produce more
ammonia (product).
• KC will increase.
52
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
THE HABER PROCESS

N2(s) + 3H2(g) 2NH3(g) ΔH = –91.8 kJ

In Haber process, low temperature will increase the yield


of ammonia, but the rate of reaction will be too low.
The usual ideal conditions for synthesis of ammonia :
Temperature : 450°C - 500°C [ optimize yield and rate ]
Catalyst : Iron [ speed up the reaction ]
Promoter : Al2O3 [ enhance the catalyst ]
Pressure : 250 atm [ save cost ] 53
53
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
Try this … 1
Lime (CaO) used primarily in the manufacture of
steel, glass, and high–quality paper. It is produced in
an endothermic reaction by thermal decomposition of
limestone:
CaCO3(s) CaO(s) + CO2(g)

How would the reaction conditions be so as to


produce the maximum amount of lime?

Answer :
Ideal conditions : low pressure, high temperature, and continual removal of
CO2, as it forms. 54
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
Try this … 2
The oxidation of SO2 to SO3 is an important industrial
reactions because it is the key in sulfuric acid production:

SO2(g) + ½O2 SO3(g) ΔH = –99.2 kJ

a) What qualitative combination of T and P maximizes


SO3 yield?
High pressure, low temperature

b) How does addition of O2 affect Q ? K ?


Q would be decreased, K would be unchanged.
55
Le Chatelier’s Principle
Application of Le Chatelier’s Principle
Try this … 2

SO2(g) + ½O2 SO3(g) ΔH = –99.2 kJ

c) Suggest a reason catalysis is used in the manufacture


of H2SO4?
A catalyst is used to increase the rate because
the low temperature needed for increased yield
would also lower the reaction rate.
Without the catalyst, a much higher temperature
would be needed to achieve the same rate and
result in a much lower yield. 56

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