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TOPICS
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Disproportionation
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Potential diagrams
7.1 Introduction
This chapter is concerned with equilibria involving oxidation
and reduction processes. Firstly, we review concepts that will
be familiar to most readers: denitions of oxidation and reduction, and the use of oxidation states (oxidation numbers).
(7.1)
2MgO
oxidation
reduction
&
FrostEbsworth diagrams
&
&
"
Oxidation states
Oxidation states can be assigned to each atom of an element in
a compound but are a formalism. We assume that readers of
this book are already familiar with this concept, but practice
is given in problems 7.1 and 7.2 at the end of the chapter.
The oxidation state of an element is taken to be zero, irrespective of whether the element exists as atoms (e.g. Ne), molecules
(e.g. O2 , P4 ) or an innite lattice (e.g. Si). In addition, in the
assignment of oxidation states to elements in a compound,
any homonuclear bond is ignored. For example, in H2 O2 , 7.1,
the oxidation state of each O atom is 1.
This reaction could be written in terms of the two halfreactions 7.2 and 7.3, but it is important to remember that
neither reaction occurs in isolation.
Mg Mg2 2e
oxidation
7:2
O2 4e 2O2
reduction
7:3
"
"
(7.1)
193
High-resistance
voltmeter
Electrons
V
Copper
foil
Electrically
conducting wire
Zinc
foil
Salt bridge
Aqueous
zinc(II) sulfate
solution
Aqueous
copper(II) sulfate
solution
Fig. 7.1 A representation of the Daniell cell. In the left-hand cell, Cu2 ions are reduced
. to copper metal, and in the right-hand
cell, zinc metal is oxidized to Zn2 ions. The cell diagram is written as: Zns j Zn2 aq..Cu2 aq j Cus.
16HCl(conc) + 2KMnO4(s)
(7.5)
Stock nomenclature
Although we write the oxidation state of Mn in MnO4 as
7, this must not be taken to imply the presence of an Mn7
ion (which, on electrostatic grounds, would be extremely
unlikely). Stock nomenclature uses Roman numerals to
indicate oxidation state, e.g.:
[MnO4 ]
[IO4 ]
[BrO3 ]
[ClF4 ]
[Co(H2 O)6 ]2
tetraoxomanganate(VII)
tetraoxoiodate(VII)
trioxobromate(V)
tetrauorochlorate(III)
hexaaquacobalt(II)
oxidation
7:6
When two such half-cells are combined in an electrical circuit, a redox reaction occurs if there is a potential dierence
between the half-cells. This is illustrated in Figure 7.1 by the
194
7:7
The two solutions in the Daniell cell are connected by a saltbridge (e.g. gelatine containing aqueous KCl or KNO3 ),
which allows the passage of ions between the half-cells without allowing the Cu(II) and Zn(II) solutions to mix too
quickly. When the Daniell cell is assembled, redox reaction
7.8 occurs spontaneously.
Zns Cu2 aq Zn2 aq Cus
"
7:8
ln K
zFE o cell
RT
The standard cell potential (at 298 K) for the Daniell cell is
1.10 V. Calculate the corresponding values of G o and K
and comment on the thermodynamic viability of the cell reaction:
Zns Cu2 aq Zn2 aq Cus
"
7:9
Go RT ln K
7:10
7:11
ln K
ln K 85:6
K 1:45 1037
The large negative value of Go and a value of K which is
1 correspond to a thermodynamically favourable reaction,
one which virtually goes to completion.
Self-study exercises
1. For the Daniell cell, log K 37:2. Calculate G o for the cell.
[Ans: 212 kJ mol1 ]
2. The value of G o for the Daniell cell is 212 kJ mol1 .
[Ans: 1.10 V]
Calculate E o cell .
3. At 298 K, E o cell for the Daniell cell is 1.10 V. Determine the
equilibrium ratio [Cu2 ]/[Zn2 ].
[Ans. 6:9 1038 ]
Go
212
RT
298 8:314 103
For an introduction to galvanic cells and the Nernst equation see: C.E.
Housecroft and E.C. Constable (2002) Chemistry, 2nd edn, Prentice
Hall, Harlow, Chapter 17; for a more detailed discussion, see: P.
Atkins and J. de Paula (2002) Atkins Physical Chemistry, 7th edn,
Oxford University Press, Oxford, Chapter 10.
7:12
7:14
7.1 is organized such that the half-cell with the most positive
E o is at the bottom of the table. The most powerful oxidizing
agent among the oxidized species in Table 7.1 is F2 , i.e. F2 is
readily reduced to F ions. Conversely, at the top of the
table, Li is the most powerful reducing agent, i.e. Li is readily
oxidized to Li .
The calculated value E o 1:23 V for the O2 , 4H /2H2 O
electrode implies that electrolysis of water using this applied
potential dierence at pH 0 should be possible. Even with a
platinum electrode, however, no O2 is produced. The
minimum potential for O2 evolution to occur is about
1.8 V. The excess potential required (0.6 V) is the overpotential of O2 on platinum. For electrolytic production of
H2 at a Pt electrode, there is no overpotential. For other
metals as electrodes, overpotentials are observed, e.g. 0.8 V
for Hg. In general, the overpotential depends on the gas
evolved, the electrode material and the current density. It
may be thought of as the activation energy for conversion
of the species discharged at the electrode into that liberated
from the electrolytic cell, and an example is given in
worked example 16.3. Some metals do not liberate H2
from water or acids because of the overpotential of H2 on
them.
7:13
Zns 2H aq Zn2 aq H2 g
195
7:15
E o 0:77 V
196
Table 7.1 Selected standard reduction potentials (at 298 K); further data are listed in
Appendix 11. The concentration of each substance in aqueous solution is 1 mol dm3
and the pressure of a gaseous component is 1 bar (105 Pa). Note that where the halfcell contains [OH] , the value of E o refers to OH 1 mol dm3 , and the notation
E o OH 1 should be used (see Box 7.1).
Reduction half-equation
E o or
E o OH 1 / V
Li aq e Lis
K aq e Ks
Ca2 aq 2e Cas
Na aq e Nas
Mg2 aq 2e Mgs
Al3 aq 3e Als
Mn2 aq 2e Mns
Zn2 aq 2e Zns
Fe2 aq 2e Fes
Cr3 aq e Cr2 aq
Fe3 aq 3e Fes
2H (aq, 1 mol dm3 2e H2 (g, 1 bar)
Cu2 aq e Cu aq
AgCls e Ags Cl aq
Cu2 aq 2e Cus
FeCN6 3 aq e FeCN6 4 aq
O2 g 2H2 Ol 4e 4OH aq
I2 aq 2e 2I aq
Fe3 aq e Fe2 aq
Ag aq e Ags
Febpy3 3 aq e Febpy3 2 aq
Br2 aq 2e 2Br aq
Fephen3 3 aq e Fephen3 2 aq
O2 g 4H aq 4e 2H2 Ol
Cr2 O7 2 aq 14H aq 6e 2Cr3 aq 7H2 Ol
Cl2 aq 2e 2Cl aq
MnO4 aq 8H aq 5e Mn2 aq 4H2 Ol
Co3 aq e Co2 aq
S2 O8 2 aq 2e 2SO4 2 aq
F2 aq 2e 2F aq
3.04
2.93
2.87
2.71
2.37
1.66
1.19
0.76
0.44
0.41
0.04
0
0.15
0.22
0.34
0.36
0.40
0.54
0.77
0.80
1.03
1.09
1.12
1.23
1.33
1.36
1.51
1.92
2.01
2.87
Self-study exercises
I2 aq 2e 2I aq
4. Write down the two half-cell reactions that combine to give the
following overall reaction:
Mgs 2H aq Mg2 aq H2 g
"
[Ans. 2.37 V]
197
Fe aq 3e Fes
Cl2 aq 2e 2Cl aq
E o 0:44 V
o
E 0:04 V
E o 1:36 V
7:16
7:17
7:18
7:19
7:20
7:22
7:23
198
3
pH dependence of a reduction
7:25
7:26
7:27
"
Self-study exercises
These questions all refer to the redox couple in the worked
example.
1. Show that E 1:25 V when pH 3.0 and the ratio
[Mn2 ] : [MnO4 ] 1 : 100.
2. For a ratio [Mn2 ] : [MnO4 ] 1000 : 1, what must the pH of
the solution be to give a value of E 1.45 V?
[Ans. 0.26]
3. For a ratio [Mn2 ] : [MnO4 ] 1 : 100, determine E in a
solution of pH 1.8.
[Ans. 1.36 V]
199
Self-study exercises
Cr3 aq e Cr2 aq
2H aq 2e H2 g
E o 0:41 V
Eo 0 V
At 298 K:
Go zFE o cell
2 96 485 0:41
79:1 103 J per mole of reaction
79:1 kJ per mole of reaction
Thus, the reaction is thermodynamically favourable, indicating that aqueous Cr2 ions are not stable in acidic (1 M),
aqueous solution. [Note: In fact, this reaction is aected by
kinetic factors and is quite slow.]
Raising the pH of the solution lowers the concentration of
H ions. Let us (arbitrarily) consider a value of pH 3.0 with
the ratio [Cr3 ] : [Cr2 ] remaining equal to 1. The 2H =H2
electrode now has a new reduction potential.
RT
1
E Eo
ln 2
zF
H
8:314 298
1
0
ln
2 96 485
1 103 2
0:18 V
Now we must consider the following combination of
half-cells, taking Cr3 =Cr2 still to be under standard
conditions:
Cr3 aq e Cr2 aq
2H aq 2e H2 g
Ecell 0:18 0:41 0:23 V
At 298 K:
G zFEcell
2 96 485 0:23
44:4 103 J per mole of reaction
44:4 kJ per mole of reaction
E o 0:41 V
E 0:18 V
E o 0:80 V
7:29
200
APPLICATIONS
Box 7.2 Reference electrodes
Equation 7.31 shows the reduction reaction that occurs in
the silver chloride/silver electrode, which is written in the
form Cl aq j AgCl j Ag (each vertical bar denotes a phase
boundary). This is an example of a half-cell which is
constructed by coating a wire of metal M with a solid salt
(MX) and immersing this electrode in an aqueous solution
containing X ions; [X ] at unit activity 1 mol dm3 for
the standard electrode.
AgCls Ag aq Cl aq
7:30
AgCls e Ags Cl aq
7:31
E o 0:268 V
3 1014
7:32
E o 0:03 V
7:33
AgI3 aq e Ags 3I aq
E o 1:54 V
7:34
201
APPLICATIONS
Box 7.3 Undersea steel structures: sacricial anodes and cathodic protection
In Chapter 5, we discussed structural and manufacturing
aspects of steel, and the fact that galvanized steel possesses
a protective Zn coating. Uses of Zn-coated steel include
ships hulls, undersea pipelines and oil-rigs, i.e. structures
that are in contact with seawater. In the presence of H2 O,
O2 and an electrolyte (e.g. seawater), steel is subject to
corrosion. There is always the possibility that coated steel
will be scratched, and that this surface imperfection will
permit rusting of the iron beneath it to occur. The Zn
coating, however, behaves as a sacricial anode. The actual
process of corrosion is not simple, but can be summarized
as follows:
Zn2 aq 2e Zns
E o 0:76 V
E o 0:44 V
7:35
Using data from equations 7.34 and 7.35, and from Table 7.1,
explain why Mn(II) is not oxidized by O2 in solutions at pH 0,
but is oxidized by O2 in solutions in which [OH ] is
1 mol dm3 .
E o 1:23 V
Mn3 aq e Mn2 aq
E o 1:54 V
First, nd the half-equations that are relevant to the question; note that pH 0 corresponds to standard conditions in
which H 1 mol dm3 .
202
Self-study exercises
1. Why is the notation E OH 1 used rather than E for the rst
two equilibria in the list above?
[Ans. See Box 7.1]
185 kJ mol1
Go 4 zFE o
3
11 kJ mol1
By Hesss Law:
Go 1 Go 4 Go 2 Go 3
Go 1 11 Go 2 185
Go 1 Go 2 174 kJ mol1
RT ln 6 RT ln 6 174
ln 6 ln 6
ln
174
RT
6
174
174
6
RT
8:314 103 298
Co3 aq e Co2 aq
Fe3 aq e Fe2 aq
E o 1:92 V
7:36
[Co(H2O)6
]2+(aq)
+ 6NH3(aq)
Go2
]2+(aq)
[Co(NH3)6
6
e70:2 3:1 1030
6
E o 0:77 V
7:38
4
E o 0:36 V
7:37
It follows from these data that the overall formation constant for CoNH3 6 3 is 1030 times greater than that for
CoNH3 6 2 as is shown below:
Go3
6
70:2
6
FeCN6 aq e FeCN6 aq
E o 0:11 V
Go1
ln
3
CoNH3 6 aq e CoNH3 6 aq
[Co(H2O)6]3+(aq) + 6NH3(aq)
70:2
+ 6H2O(l)
7:39
For a full discussion, see: M. Gerloch and E.C. Constable (1994) Transition Metal Chemistry: The Valence Shell in d-Block Chemistry, VCH,
Weinheim, p. 176178.
203
Self-study exercises
2Cu+(aq)
Cu2+(aq) + Cu(s)
(7.40)
oxidation
reduction
3[MnO4]2(aq) + 4H+(aq)
2[MnO4](aq) + MnO2(s) + 2H2O(l)
(7.41)
oxidation
reduction
Reaction 7.40 takes place when Cu2 SO4 (prepared by reacting Cu2 O and dimethyl sulfate) is added to water, while
reaction 7.41 occurs when acid is added to a solution of
K2 MnO4 . Equilibrium constants for such disproportionation reactions can be calculated from reduction potentials
as in worked example 7.6.
E o 0:15 V
E o 0:34 V
(3) Cu aq e Cus
E o 0:52 V
0:37 V
E o 0:56 V
3
1 96 485 0:37 10
35:7 kJ per mole of reaction
7:43
7:44
35:7
8:314 103 298
K 1:81 106
7:42
Go
ln K
RT
E o 1:19 V
Mn3 aq e Mn2 aq
E o 1:51 V
7:45
E o 1:54 V
7:46
204
E o 1:69 V
7:47
3HMnO4 aq H aq
MnO2 s 2MnO4 aq 2H2 Ol
[MnO4]
Self-study exercise
+0.90
[HMnO4]
+2.10
7:48
MnO2
MnO4 aq H aq e HMnO4 aq
Eo 0:90 V
HMnO4 aq 3H aq 2e MnO2 s 2H2 Ol
Eo 2:10 V
Combining these two half-cells gives reaction 7.48 for
which E o cell 1:20 V and Go 298 K 231 kJ mol1 .
This indicates that reaction 7.48 is spontaneous. Similarly,
at pH 0, Mn3 is unstable with respect to disproportionation
to MnO2 and Mn2 (equation 7.49).
2Mn3 aq 2H2 Ol Mn2 aq MnO2 s 4H aq
7:49
We saw in Section 7.2 that the value of the reduction
potential for a half-reaction depends on cell conditions,
and where the half-reaction involves H or [OH] ions, the
reduction potential varies with pH. Moreover, the extent of
variation depends on the number of moles of H or [OH]
per mole of reaction. It follows that the potential diagrams
in Figure 7.2 are appropriate only at the stated pH values;
a new potential diagram is needed for every value of
pH, and, therefore, caution is needed when using these
diagrams.
+1.51
[MnO4]
+0.90
[HMnO4]
+2.10
MnO2
+0.95
+1.69
Mn3+
+1.54
Mn2+
[MnO4]
+0.56
[MnO4]2
Mn
+1.23
+0.59
1.19
+0.27
0.04
[MnO4]3
+0.93
MnO2
+0.15
Mn2O3
0.23
Mn(OH)2
1.56
Mn
+0.60
Fig. 7.2 Potential diagrams (Latimer diagrams) for manganese in aqueous solution at pH 0 (i.e. H 1 mol dm3 ), and in
aqueous solution at pH 14. For such diagrams, it is essential to specify the pH, and the reason is obvious from comparing the
two diagrams.
205
Self-study exercises
1. Although the method given here is probably the safest way to
perform the calculation, substitution of a value for the Faraday
constant may in fact be excluded. Why?
2. Construct a potential diagram for the reduction of aqueous Cr3
to Cr2 , followed by reduction to Cr. Values of E o for the
Cr3 =Cr2 and Cr2 /Cr couples are 0.41 and 0.91 V,
respectively. Calculate E o for the Cr3 /Cr couple.
[Ans. 0.74 V]
3. Construct a potential diagram (at pH 0) for the reduction of
aqueous HNO2 to NO and then to N2 O given that E o for the
HNO2 /NO and NO/N2 O couples are 0.98 and 1.59 V
respectively. Calculate E o for the following half-reaction:
2HNO2 aq 4H aq 4e N2 Og 3H2 Ol
[Ans. 1.29 V]
Fe3+(aq)
+0.77
Fe2+(aq)
0.44
Eo
Go
zF
10:6
3 96 485 103
0:04 V
Go
2:38 V
F
A.A. Frost (1951) Journal of the American Chemical Society, vol. 73,
p. 2680; E.A.V. Ebsworth (1964) Education in Chemistry, vol. 1, p. 123.
206
Go
1:54 2:38 0:84 V
F
Go
0:95 1:54 2:38 0:11 V
F
Gradient of line
2:38
1:19 V
A positive gradient between two points indicates that E o
for the corresponding reduction process is positive, and
207
Fig. 7.4 FrostEbsworth diagrams in aqueous solution at pH 0, i.e. [H ] 1 mol dm3 , for (a) chromium, (b) phosphorus and
(c) nitrogen.
208
By drawing lines between the points for PH3 and H3 PO3 , and
between H3 PO3 and H3 PO4 , you can see that H3 PO2 is
unstable with respect to disproportionation, either to PH3
and H3 PO3 , or to PH3 and H3 PO4 . This illustrates the
fact that you should look beyond the lines that are already
represented in a given FrostEbsworth diagram.
Self-study exercises
Use Figures 7.4b and 7.4c to answer these questions; both
diagrams refer to the same aqueous solution conditions.
1. On going from N to P, how does the thermodynamic stability of
the 5 oxidation state alter?
2. What do the diagrams tell you about the thermodynamic
stability of N2 and of P4 with respect to other N- or Pcontaining species?
3. Estimate values for E o N2 =NH3 OH and E o NH3 OH =N2 H5
and comment on the thermodynamic stability of [NH3 OH]
in aqueous solution at pH 0.
[Ans. 1:8 and 1.4 V respectively]
Mz+(aq) + ze
Step (1)
Dehydration of the
metal ion
M(g)
Step (2)
IE
E o 2:71 V
Ag aq e Ags
E o 0:80 V
7:50
7:51
H+(aq) + e
M(s)
Step (3)
aHo
Mz+(g)
Step (1)
Dehydration of the
hydrogen ion
1/
2H2(g)
Step (3)
aHo
H+(g)
H(g)
Step (2)
IE1
Fig. 7.5 The half-reaction for the reduction of Mz ions to M, or H to 12H2 , can be considered in terms of three contributing
steps for which thermodynamic data may be determined independently.
Chapter 7 . The relationships between standard reduction potentials and some other quantities
209
Table 7.2 Factors determining the magnitude of the standard reduction potentials for the Na /Na and Ag /Ag couples in aqueous
solution (pH 0); steps (1), (2) and (3) are dened in Figure 7.5.
Redox couple
Overall H o
/ kJ mol1
Calculated E o
/V
Na /Na
H / 12 H2
Ag /Ag
404
1091
480
492
1312
733
108
218
285
196
439
538
2.52
0
1.03
Go zFE o
X2 2e 2X
f Go Na ;aq
X F; Cl; Br; I
7:52
E o 2:71 V
e Br aq
E o 1:09 V
1
2 Br2 l
f Go Br ;aq
96 485 2:71
261:5 kJ mol1
1000
96 485 1:09
105:2 kJ mol1
1000
Table 7.3 Factors determining the magnitude of the standard reduction potentials for the Cu2 /Cu and Zn2 /Zn couples in aqueous
solution (pH 0); steps (1), (2) and (3) are dened in Figure 7.5.
Redox couple
Overall H o
/ kJ mol1
Calculated E o
/V
Zn2 /Zn
H / 12 H2
Cu2 /Cu
2047
1091
2099
2644
1312
2702
130
218
338
727
439
941
0.78
0
0.33
210
Self-study exercises
See Appendix 11 for values of E o .
1. Calculate the value of sol G o (298 K) for NaCl given that
[Ans. 8.7 kJ mol1 ]
f G o (NaCl,s) is 384.0 kJ mol1 .
2. sol G o (298 K)
for
NaF 7:9 kJ mol1 .
Determine
o
[Ans. 546.3 kJ mol1 ]
f G (NaF,s) at 298 K.
3. Given that sol G o (298 K) for KI is 9.9 kJ mol1 , calculate
f G o (KI, s) at 298 K.
[Ans. 324.9 kJ mol1 ]
7:53
"
O2 ;
C or CO;
7:54
"
Ellingham diagrams
The choice of a reducing agent and the conditions for a
particular extraction process can be assessed by using an
Ellingham diagram such as that in Figure 7.6. This illustrates
how f Go for a range of metal oxides and CO varies with
temperature. In order that values are mutually comparable,
f Go refers to the Gibbs energy of formation per half-mole
of O2 . Thus for SrO, f Go refers to reaction 7.55, and for
Al2 O3 it corresponds to reaction 7.56.
Sr 12 O2 SrO
7:55
2
3 Al
7:56
"
"
1
3 Al2 O3
In Figure 7.6, each plot is either linear (e.g. NiO) or has two
linear sections (e.g. ZnO); for the latter, there is a change in
gradient at the melting point of the metal.
Three general results arise from Figure 7.6:
. as the temperature increases, each metal oxide becomes
less thermodynamically stable (less negative f Go );
"
"
"
SnO2 C Sn CO2
12 O2
Other data could have been plotted, e.g. values of f G per mole of O2 .
Consistency is the keyword!
Glossary
The following terms were introduced in this chapter.
Do you know what they mean?
q oxidation
Chapter 7 . Problems
q
q
q
q
q
q
q
q
q
q
q
q
q
q
reduction
oxidation state (oxidation number)
half-reaction (half-equation)
electrolytic cell
galvanic cell
standard conditions for a half-cell
standard hydrogen electrode
standard reduction potential, E o
standard cell potential, E o cell
overpotential
Nernst equation
potential diagram (Latimer diagram)
FrostEbsworth diagram
Ellingham diagram
211
Further reading
Nernst equation
Problems
7.1
7.2
7.4
7.5
7.6
"
"
"
7.3
"
"
"
"
"
"
212
7.7
CuCls Cu aq Cl aq
K 1:81 106
Ksp 1:72 107
What does the value of Go tell you about the tendency of
precipitated CuCl to disproportionate?
7.16 Using appropriate data from equations 7.42 to 7.46,
7.9
0.001
0.252
0.005
0.272
0.010
0.281
0.050
0.302
[UO2]2+
+0.06
[UO2]2+
+0.61
U4+
0.61
U3+
1.80
+0.33
17
Ag =Ag
, and
0:80 V, calculate E for the reduction step:
AgIs e Ags I aq
and hence conrm the statement in Section 7.3 that
reduction of silver(I) when in the form of solid AgI is
thermodynamically less favourable than reduction of
AgCl.
[ClO3]
+1.15
ClO2
+1.28
HClO2
7.12 Using data from Table 7.1 and from Section 7.3, explain
3
Eo
Fe3 aq e Fe2 aq
E o 0:77 V
7.22 Use the data in the potential diagram shown in Figure 7.7
[ClO4]
+1.19
[ClO3]
+1.15
ClO2
+1.28
HClO2
+1.65
HClO
+1.61
+1.36
Cl2
Fig. 7.7 Potential diagram (Latimer diagram) for chlorine in aqueous solution at pH 0, i.e. [H ] 1 mol dm3 .
Cl
Chapter 7 . Problems
Overview problems
7.23 Use the data in Appendix 11 to rationalize the following
calculate E
O3 =O2 .
Eo
+0.66
O3
O3
O2
+1.25
Appendix 11.
(a) Determine EZn2 =Zn (at 298 K) for a half-cell in which
[Zn2 ] 0.25 mol dm3 .
(b) Calculate the reduction potential for the halfreaction:
VO2 aq 2H aq e V3 aq H2 Ol
if the ratio of the concentrations of [VO]2 : V3 is 1 : 2
and the pH of the solution is 2.2.
7.27 (a) Use appropriate data from Appendix 11 to
E o 0:40 V
E o 1:03 V
(c) How valid is Figure 7.4a for aqueous solutions at
pH 2?
[IO3]
[IO3]
+1.14
+1.23
HOI
[ICl2]
213
+1.44
+1.06
I2
I2
"
"
"
"
"
"
"