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IAL Edexcel Chemistry Unit 5 (WCH15):

Transition Metals and Organic Nitrogen


Chemistry (Part 1/5)
REALLYACADEMICS
Preface
● This series will be divided into 5 parts corresponding to the 5 topics in the 2018 specification
○ PART 1 - TOPIC 16: Redox Equilibria
○ PART 2 - TOPIC 17: Transition Metals and their Chemistry
○ PART 3 - TOPIC 18: Organic Chemistry: Arenes
○ PART 4 - TOPIC 19: Organic Nitrogen Compounds: Amines, Amides, Amino Acids and Proteins
○ PART 5 - TOPIC 20: Organic Synthesis
● This series will provide you with a means of last minute revision on [WCH15] IAL Edexcel
Chemistry Unit 5
● This series will aim to provide you with an revision in under 50 MINS
● All information here is a summary of the New Specification Book
● This series will not serve as a primary study material but as an adjunct to help you recall and
prepare as a last minute revision
● YOU CAN ALSO SUPPLEMENT THIS WITH MY OTHER VIDEOS ON FREQUENTLY ASKED
QUESTIONS OF UNIT 5
Syllabus
1. Understand the terms ‘oxidation’ and ‘reduction’ in terms of electron transfer and changes in oxidation
number, applied to s-, p- and d-block elements
2. Know what is meant by the term ‘standard electrode potential’, E
3. Know that the standard electrode potential, E, is measured in conditions of:
a. 298 K temperature
b. 100 kPa pressure of gases
c. 1.00 mol dm-3 concentration of ions
4. Know the features of the standard hydrogen electrode and understand why a reference electrode is
necessary
5. Understand that different methods are used to measure standard electrode potentials of:
a. Metals or non-metals in contact with their ions in aqueous solution
b. Ions of the same element with different oxidation numbers
6. Be able to calculate a standard emf, Ecell , by combining two standard electrode potentials
7. Be able to write cell diagrams using the conventional representation of half-cells
8. Understand the importance of the conditions when measuring an electrode potential, E
9. Be able to use standard electrode potentials to predict the thermodynamic feasibility of a reaction
Syllabus
10. Understand that Ecell is directly proportional to the total entropy change and to lnK for a reaction

11. Understand the limitations of predictions made using standard electrode potentials, in terms of kinetic stability of
systems and departure from standard conditions

12. Know that standard electrode potentials are sometimes referred to as standard reduction potentials and can be listed as
an electrochemical series

13. Understand how standard electrode potentials can be used to predict the thermodynamic feasibility of
disproportionation reactions

14. Be able to carry out both structured and unstructured titration calculations involving redox reactions, including iron(II)
ions and potassium manganate(VII) and sodium thiosulfate and iodine

15. Be able to discuss the uncertainty of measurements and their implications for the validity of the final results

16. Understand that fuel cells use the energy released on the reaction of a fuel with oxygen to generate a voltage Knowledge
that methanol and other hydrogen-rich fuels are used in fuel cells is expected.

17. Know the electrode reactions that occur in a hydrogen-oxygen fuel cell
1. Understand the terms ‘oxidation’ and ‘reduction’ in terms of electron transfer and
changes in oxidation number, applied to s-, p- and d-block elements
2. Know what is meant by the term ‘standard electrode potential’, E
3. Know that the standard electrode potential, E, is measured in conditions of:
A. 298 K temperature
B. 100 kPa pressure of gases
C. 1.00 mol dm-3 concentration of ions
4. Know the features of the standard hydrogen electrode and understand why a
reference electrode is necessary
5. Understand that different methods are used to measure standard electrode
potentials of:
A. Metals or non-metals in contact with their ions in aqueous solution
B. Ions of the same element with different oxidation numbers
12. Know that standard electrode potentials are sometimes referred to as standard
reduction potentials and can be listed as an electrochemical series
Redox
● Oxidation: ● Reduction:
○ Loss of electrons ○ Gain of electrons
○ Loss of oxygen ○ Gain of oxygen
○ Gain of hydrogen ○ Loss of hydrogen
○ Gain of oxidation number ○ Loss of oxidation number

● Blocks of the periodic table, such as the s-block and d-block, indicate
the orbital of the outer electrons.
● During reactions, s-block, d-block and some p-block species tend to
undergo oxidation whereas p-block elements tend to undergo
reduction
Absolute potential difference
● Definition: The potential difference between a metal
and a solution of its ions
● When a metal such as magnesium or copper is placed
in water, they have a tendency to lose electrons to
form positive ions:

● A layer of positive ions forms around the metal rod


and some of the positive ions regains electrons.
Hence, there is a dynamic equilibrium between the
rate at which ions are formed and the rate at which
the ions regain electrons to turn into an atom again.
Absolute potential difference (Continued…)
● When the equilibrium is shifted to one side, there is a difference in
potential between the metal and the solution.
○ If there is a stronger shift of equilibrium, there is a greater change of potential difference.
○ This potential difference between the metal and the solution is known as the absolute
potential difference
● Is it possible to measure the ABSOLUTE potential difference of a metal
and its solution?
○ NO, because there needs to be two metals connected to the two terminals in the
voltmeter. If there are two different metals, the voltmeter will measure the potential
difference between the two metals but not the metal and the solution.
○ This solve this problem, we would need a reference electrode.
Reference electrode (Standard Hydrogen Electrode)
● The reference electrode is a
standard hydrogen electrode.
● This electrode consists of:
○ Hydrogen gas at a pressure of 100 kPa
○ Platinum foil
○ Solution of HCl with a hydrogen ion
concentration of 1 mol dm-3
○ Temperature of 298K
● This cell will have potential of 0.00V
and can be used to find the
potential difference of different
metals.
Standard conditions
● The standard conditions are:
○ Gas pressure, 100kPa
○ Temperature, 298K
○ Concentration of ions in solution, 1 mol dm-3
● We need to set standard conditions because a change in these conditions
will affect the equilibrium which will affect the potential difference
Measuring a standard electrode potential
Example: Measuring the standard electrode potential of magnesium.
● The two components of the apparatus are
known as half-cells
○ They are combined to make a complete cell
● The salt bridge is needed to complete the
electrical circuit.
○ Contains a concentrated solution of potassium nitrate
in the form of liquid or a gel.
○ Theoretically, any ions can be used as long as it does
not react with the ions present in the solution.
● High-resistance voltmeter is used because it
resists the flow of electrons in the external
circuit so that the reading can represent the
difference in potential difference between the
two half-cells when both reaction are in
equilibrium.
Standard Electrode Potential
● It is the emf measured when a half-cell is connected to a standard
hydrogen electrode under standard conditions.
● Positive potentials mean that substances are more easily reduced and will
gain electrons and the equilibrium will more likely shift to the right.

● Negative potentials mean the substances are more easily oxidised and
will lose electrons and the equilibrium will more likely shift to the left.
Measuring standard electrode potentials of more complicated
redox systems
● Systems involving gases:
○ Example: Chlorine
■ Set up a half-cell in which Cl gas is
bubbled into a solution containing
chloride ions and place a piece of
platinum into the solution
■ The other terminal is connected to
a standard hydrogen electrode.
Measuring standard electrode potentials of more complicated
redox systems
● Systems involving gases:
○ Example: Chlorine
■ Set up a half-cell in which Cl gas is
bubbled into a solution containing
chloride ions and place a piece of
platinum into the solution
■ The other terminal is connected to
a standard hydrogen electrode.
Measuring standard electrode potentials of more complicated
redox systems
● Systems involving:
1. Non-metal elements and their ions in solution
2. Ions of the same element with different oxidation
numbers
○ These systems containing both the
element and ions in the solution.
■ For example: Br2 and Br- ions in the
solution or Fe2+ and Fe3+ ions in the
solution
All you gotta know…
● The more negative the E value, ● The more positive the E value, the
the more the equilibrium position more the equilibrium position lies
lies towards the left - and the towards the right - and the more
more readily the species on the readily the species on the left
right loses electrons. gains electrons.
● The more negative the E value, ● The more positive the E value, the
the more powerful the reducing more powerful the oxidising
agent. agent.
Summary table
6. Be able to calculate a standard emf, Ecell , by combining
two standard electrode potentials
7. Be able to write cell diagrams using the conventional
representation of half-cells
Electrochemical Cells
● Electrochemical cells is a device for producing an electric current from chemical
reactions.
● For example: Construction of an electrochemical cell with Zn2+| Zn half cell and Cu2+ |
Cu half cell under standard conditions

➔ Here are the two relevant standard


electrode potentials:

➔ The E value for Zn half cell is more


negative, so the zinc electrode will be
the negative electrode.
◆ So the Zn atom will lose electrons and transfer
it to the Cu ion.
Electrochemical Cells (Continued…)
● Electrochemical cells is a device for producing an electric current from chemical
reactions.
● For example: Construction of an electrochemical cell with Zn2+| Zn half cell and Cu2+ |
Cu half cell under standard conditions
Conventional Cell Representation
● Cells are represented in a simplified way so that they don’t have to be
drawn out each time. This representation has specific rules to help show
the reactions that occur:
○ The half-cell with the most negative potential goes on the left
○ The most oxidised species from each half-cell goes next to the salt bridge
○ A salt bridge is shown using a double dotted lines
○ State symbols are always included
● For example: cell of Zn2+(aq) | Zn(s) and Cu2+(aq) | Cu(s)
Conventional Cell Representation (Continued…)
● When the electrode, i.e. The electrical connection between the solution
and the external circuit, is a piece of platinum foil, the following
conventional is used:

○ Notice that because there is no phase boundary between Fe3+(aq) and Fe2+(aq), a comma
is used to separate them, not a solid vertical line.
● The standard hydrogen electrode is represented as follows:
8. Understand the importance of the conditions when measuring an
electrode potential, E
9. Be able to use standard electrode potentials to predict the
thermodynamic feasibility of a reaction
10. Understand that Ecell is directly proportional to the total entropy
change and to lnK for a reaction
11. Understand the limitations of predictions made using standard
electrode potentials, in terms of kinetic stability of systems and
departure from standard conditions
13. Understand how standard electrode potentials can be used to
predict the thermodynamic feasibility of disproportionation reactions
Is the reaction thermodynamically feasible?
● Thermodynamically feasible reaction - A reaction that should take
place without any intervention by us, if we consider the enthalpy and
entropy changes involved.
● This can be found out by calculating the overall cell emf using the
following formula:

○ If the overall cell potential is a positive value, the reaction taking place is spontaneous and
favourable. The more positive the potential, the more favourable the reaction.
Worked example 1
Will zinc displace copper when added to a aqueous solution containing copper
ions?
Answer 3. The cell representation can be written as:

1. The proposed reaction is:


4. The total of the cell would be:
Zn(s) + Cu2+(aq) —> Zn2+(aq) + Cu(s)
● E(cell) = +0.34 - (-0.76)
2. The two standard electrode potentials to ● E(cell) = +1.10V
consider are:

5. Because the value for Ecell is positive, the reaction


is feasible
Worked example 2
Will copper produce hydrogen gas when added to dilute sulfuric acid?

Answer
3. The cell representation can be written as:

1. The proposed reaction is:


4. The total of the cell would be:
Cu(s) + 2H+(aq) —> Cu2+(aq) + H2(g)
● E(cell) = -0.34 - (0)
2. The two standard electrode potentials to ● E(cell) = -0.34V
consider are:

5. Because the value for Ecell is negative, the reaction


is not feasible
Effects of Concentration and Pressure
● The conditions are important when measuring the standard cell potential
because changing the conditions will change the emf value obtained.
○ Increasing the concentration of the solutions used in the electrochemical cell makes
the cell emf more positive as fewer electrons are produced in the reaction.
○ Increasing the pressure of the cell will make the cell emf more negative as more
electrons are produced
Summary
● The thermodynamic feasibility of a chemical reaction can be predicted
using standard electrode potentials
● Although the standard electrode potentials indicate that a reaction is
thermodynamically feasible, it may not take place for two reasons:
○ The reactants may be kinetically stable because the activation energy for the reaction is
very large, and
○ The reaction may not be taking place under standard conditions.
● A reaction that is not thermodynamically feasible under standard
conditions may become feasible when the conditions are altered
● Changing the conditions may alter the electrode potential, E, of a half-cell
because the position of equilibrium of the half-cell reaction may change
Disproportionation
● In a disproportionation reaction, a species is both oxidised and reduced.
● Electrode potentials can be used to assess whether a species will undergo
disproportionation. If the overall Ecell value is positive, then the
disproportionation reaction is feasible.
Ecell and Entropy
● The standard emf of a cell is directly proportional to both ln(K), where K is
the equilibrium constant of the reaction, and the total entropy change,
(ΔStotal). This means that a positive Ecell value will have an overall positive
entropy change.
Limitations
● There are limitations to both calculating a standard cell potential using
the SHE and using the calculated value to determine reaction feasibility
● Although the cell emf value will tell you if a reaction is thermodynamically
feasible or not, it does not take into account the kinetics of the reaction.
Even if a reaction is feasible, it may occur at such a slow rate that, in
practice, it does not actually occur.
● The standard cell potential relies on conditions being standard
throughout the experiment, when in reality, the system may deviate from
standard conditions
14. Be able to carry out both structured and unstructured
titration calculations involving redox reactions, including
iron(II) ions and potassium manganate(VII) and sodium
thiosulfate and iodine
15. Be able to discuss the uncertainty of measurements
and their implications for the validity of the final results
Titration of Potassium Manganate(VII) with Iron(II) ions
● In this reaction, the iron(II) ions are oxidised and the manganate(VII) ions
are reduced.
● The ionic half-equations involved are:
○ MnO4-(aq) + 8H+(aq) + 5e- —> Mn2+(aq) + 4H2O(l)
○ Fe2+(aq) —> Fe3+(aq) + e-
● The overall equation for the reaction is:
○ MnO4-(aq) + 8H+(aq) + 5Fe2+(aq) —> Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)
● An aqueous solution containing MnO4- ions is purple, concentrated
solutions of Mn2+ is pale pink, Fe2+ is pale green and Fe3+ is yellow.
● However, the solutions used in titrations are usually so dilute that they
appear colourless.
Titration of Potassium Manganate(VII) with Iron(II) ions
(Continued…)
● The method of performing the titration is:
○ Pipette an accurately measured volume, usually 25cm3 of the iron(II) solution into a
conical flask and then add a small volume of dilute sulfuric acid.
○ Slowly add potassium manganate(VII) solution of accurately known concentration from a
burette and swirl the mixture
○ The potassium manganate(VII) solution will turn colourless until all of the iron(II) ions have
been oxidised
○ The addition of one more drop of potassium manganate(VII) solution will turn the mixture
pale pink
Redox Titrations with Iodine and Sodium Thiosulfate
● Thiosulfate ions reduce iodine to iodide ions.
● The ionic half-equations involved are:
○ 2S2O32-(aq) —> S4O62-(aq) + 2e-
○ I2(aq) + 2e- —> 2I-(aq)
● The overall equation for the reaction is:
○ 2S2O32-(aq) + I2(aq) —> S4O62-(aq) + 2I-(aq)
● The indicator used in titrating iodine with sodium thiosulfate is starch
solution.
○ With free iodine, it produces a deep blue-black colour.
○ The blue-black colour disappears as soon as sufficient sodium thiosulfate has been added
to react with all of the iodine
Redox Titrations with Iodine and Sodium Thiosulfate
(Continued…)
● The procedure is as follows:
○ Add sodium thiosulfate solution from the burette to the iodine solution until the original
brown colour of the iodine changes to pale yellow
○ Add a few drops of starch solution to produce a blue coloration
○ Add the sodium thiosulfate solution drop by drop until the blue-black solution turns
colourless.
Errors and Uncertainty
● When using apparatus in experiments, no measuring instrument is 100%
accurate - there is always some degree of uncertainty in the value recorded.
● The percentage uncertainty of a measurement can be calculated if the
uncertainty of the instrument is known.

● The error in apparatus measurements has implications for validity. This relates
to how close the answer is to the true answer.
● The best way of reducing uncertainties in a titration is to increase the titre
volume needed for the reaction.
16. Understand that fuel cells use the energy released on
the reaction of a fuel with oxygen to generate a voltage
Knowledge that methanol and other hydrogen-rich fuels
are used in fuel cells is expected.
17. Know the electrode reactions that occur in a
hydrogen-oxygen fuel cell
Fuel cells
● Electrochemical cells can be a useful source of energy for commercial use.
They can be produced to be non-rechargeable, rechargeable or fuel cells.
● Fuel cells are a type of electrochemical cell used to generate an electrical
current without needing to be recharged. In fuel cells, a fuel undergoes
combustion in oxygen and the energy released is used to generate a
voltage.
● The most common type of fuel cell is the hydrogen fuel cell.
Hydrogen-Oxygen Fuel Cell
● Hydrogen is supplied externally as a gas, and the cell can operate as long as the fuel supply is maintained.
● In the hydrogen-oxygen fuel cell, both metal electrodes are coated with platinum, which catalyses the
reactions that take place at the electrodes.
● The reaction can take place in both acidic or alkaline electrolyte
● The hydrogen ions pass through the proton exchange membrane, which allows them to enter the
compartment containing the positive electrode, where they can react with oxygen.

In an acidic In an alkaline
electrolyte: electrolyte:
Hydrogen-Oxygen Fuel Cell (Continued…)
● Advantages of ● Disadvantages of
hydrogen-oxygen fuel cells: hydrogen-oxygen fuel cells:
○ They offer an alternative to the ○ High flammability of hydrogen
direct use of fossil fuels such as ○ Expensive to produce
petrol and diesel
○ Does not contribute the global
warming or acid rain
○ They are lighter and more
efficient than engines that use
fossil fuels
Exam Practice Questions
Exam practice question 1
Exam practice question 1: Answer
Exam practice question 2

What is observed when a few drops of acidified hydrogen peroxide solution are added to an
excess of aqueous potassium iodide?
A. The solution turns brown and effervescence occurs
B. The solution turns brown with no effervescence
C. The solution does not change colour and effervescence occurs
D. The solution does not change colour and no effervescence occurs
Exam practice question 2: Answer

What is observed when a few drops of acidified hydrogen peroxide solution are added to an
excess of aqueous potassium iodide?
A. The solution turns brown and effervescence occurs
B. The solution turns brown with no effervescence
C. The solution does not change colour and effervescence occurs
D. The solution does not change colour and no effervescence occurs

Answer

● B because I2 formed in the solution and no gas produced


Exam practice question 3
From the following two standard electrode (redox) potentials:

It can be predicted that chloride ions will not be oxidised by solid manganese(IV) oxide.

In fact, chlorine can be prepared by heating manganese(IV) oxide with concentrated hydrochloric
acid.

Why does this prediction fail?

A. The reaction does not produce manganese(II) ions


B. The standard electrode (redox) potentials apply only if one mole of manganese(IV) oxide is used
C. The manganese(IV) oxide needs to be in alkaline solution
D. Standard electrode (redox) potentials apply only under specified conditions of concentration
and temperature.
Exam practice question 3: Answer
From the following two standard electrode (redox) potentials:

It can be predicted that chloride ions will not be oxidised by solid manganese(IV) oxide.

In fact, chlorine can be prepared by heating manganese(IV) oxide with concentrated hydrochloric
acid.

Why does this prediction fail?

A. The reaction does not produce manganese(II) ions


B. The standard electrode (redox) potentials apply only if one mole of manganese(IV) oxide is used
C. The manganese(IV) oxide needs to be in alkaline solution
D. Standard electrode (redox) potentials apply only under specified conditions of concentration
and temperature.
Exam practice question 4A
The table shows the formulae of some vanadium ions that can exist in
aqueous solution, together with the colour of each ion.

Complete the table by inserting the oxidation numbers


Exam practice question 4A: Answer
The table shows the formulae of some vanadium ions that can exist in
aqueous solution, together with the colour of each ion.

Complete the table by inserting the oxidation numbers


Exam practice question 4B
The table shows the formulae of some
vanadium ions that can exist in aqueous
solution, together with the colour of each ion.

Iron powder is added to an acidified solution


solution of ammonium vanadate(V), NH4VO3,
and the mixture is shaken until no further
change takes place.

Use the following data to explain what you


would expect to observe in the sequence of
reactions that take place. Your answer should
consider all of the electrode reactions listed.
Exam practice question 4B: Answer
Answer

● Colour changes from yellow —> blue —> green —>


violet
● VO3- (yellow) is reduced to VO2+ (green) because
○ the E value of half-cell 5 is more negative than that of
half-cell 4
○ therefore a positive Ecell value
● VO2+ is then reduced to V3+ (blue) because
○ E value of half-cell 5 is more negative than that of
half-cell 3
○ therefore a positive Ecell value
● V3+ is then reduced to V2+ (violet) because
○ E value of half-cell 5 is more negative than of half-cell 2
○ therefore a positive Ecell value
● The reduction will stop at V2+ because
○ E value of half-cell 5 is less negative than that of half-cell
1
○ therefore a negative Ecell value
Exam practice question 5A
Draw a suitably labelled diagram to show how you would measure the
standard electrode potential of the Cu2+ (aq) | Cu (s) half-cell
Exam practice question 5A: Answer
Draw a suitably labelled diagram to show how you would measure the
standard electrode potential of the Cu2+ (aq) | Cu (s) half-cell
Exam practice question 5B
The able contains some standard electrode (redox) potentials involving copper
and its ions

I. Use the data in the table to explain why the following reaction is likely to
occur

II. Use oxidation numbers to explain why this reaction is classified as a


disproportionation reaction.
Exam practice question 5B: Answer
The able contains some standard electrode (redox) potentials involving copper
and its ions

I. Use the data in the table to explain why the following reaction is likely to
occur
Answer
● E value of equation 1 is more negative than that of reaction 3 so the E
value of the cell is positive meaning that a reaction could occur.
Exam practice question 5B: Answer
The able contains some standard electrode (redox) potentials involving copper and
its ions
I. Use the data in the table to explain why the following reaction is likely to occur
II. Use oxidation numbers to explain why this reaction is classified as a
disproportionation reaction.

Answer

Disproportionation reaction states that an element is both oxidised AND reduced.

We can see here that Cu+ (+1 oxidation number) is both oxidised to Cu2+ (+2
oxidation number) and reduced to Cu (0 oxidation number)
Exam practice question 6 [Part 1]
The diagram shows a hydrogen-oxygen fuel
cell
A. Identify the particles represented by A
and B
B. The two electrodes are coated with metal
catalyst. Name a suitable metal to use as
the catalyst.
C. State two advantages of fuel cells over the
use of fossil fuels in cars
D. Apart from cost, state two disadvantages
of using fuel cells rather than fossil fuels
in cars
Exam practice question 6 [Part 1]: Answer
The diagram shows a hydrogen-oxygen fuel cell

A. Identify the particles represented by A and B


● A: electrons
● B: H+ ions
B. The two electrodes are coated with metal catalyst.
Name a suitable metal to use as the catalyst.
● Platinum
C. State two advantages of fuel cells over the use of fossil
fuels in cars
● An alternative to fossil fuels
● Does not produce greenhouse gas
● Engines are relatively light and more efficient than fossil
fuel engines
D. Apart from cost, state two disadvantages of using fuel
cells rather than fossil fuels in cars
● Limited lifetime so need regular replacement
● Storage tanks are very large and heavy
Exam practice question 6 [Part 2]
The zinc-silver oxide cell is used in button cells for watch batteries. It is based
on the following half-cell reactions:

A. Write the cell diagram for this cell


B. Write the equation for the overall reaction taking place in the cell when it
is in use. Include state symbols.
C. Calculate the standard emf, Ecell, of the cell
D. Use your answer to part C to calculate the equilibrium constant, K, for the
reaction at 298K.
Exam practice question 6 [Part 2]: Answer
The zinc-silver oxide cell is used in button cells for watch batteries. It is based
on the following half-cell reactions:

A. Write the cell diagram for this cell


● Zn (s) | Zn2+ (aq) :: Ag2O (s), H2O (l)|Ag (s), OH- (aq)
B. Write the equation for the overall reaction taking place in the cell when it
is in use. Include state symbols.
● Zn(s) + Ag2O(l) + H2O(l) —> Zn2+(aq) + 2Ag(s) + 2OH-(aq)
C. Calculate the standard emf, Ecell, of the cell
● Emf = (0.34 - - 0.76) = 1.10V
D. Use your answer to part C to calculate the equilibrium constant, K, for the reaction at 298K.
Exam practice question 6 [Part 2]: Answer
The zinc-silver oxide cell is used in button cells for watch batteries. It is based
on the following half-cell reactions:

A. Write the cell diagram for this cell


B. Write the equation for the overall reaction taking place in the cell when it is in use. Include state symbols.
C. Calculate the standard emf, Ecell, of the cell

D. Use your answer to part C to calculate the equilibrium constant, K, for the
reaction at 298K.
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