280

Journal of Nuclear Materials 130 (1985) 280.286

North-Holland, Amsterdam

THE HYDROLYSIS

OF IODINE:

Donald A. PALMER,

Chemistry

EQUILIBRIA

Richard

Division,

AT HIGH TEMPERATURES*

W. RAMETTE+,

and Robert E. MESMER

Oak Ridge National

Laboratory,

P.O. Box X, Oak Ridge, TN

37831 USA

The hydrolysis (or disproportionation)

of molecular iodine to form iodate and iodide ions has been
studied by emf measurements over the temperature range, 3.8 to 209.O'C.
The interpretation of
these results required a knowledge of the formation constant for triiodide ion and the acid dissociation constant of iodic acid, both of which were measured as a function of temperature.
The
resulting thermodynamic data have been incorporated into a general computer model describing the
hydrolysis equilibria of iodine as a function of initial concentration,
pH and temperature.
1. INTRODUCTION
The Three Mile Island nuclear
focussed
iodine

renewed attention

in aqueous

sequently

of its volatile

iodine

I2 and hypoiodous

of

For it was sub-

that hydrolysis

either

has

on the behavior

solution.

realized

accident

of iodine in

forms, namely molecular

acid HOI, would sub-

Although
processes,
radicals,

undoubtedly

a nuclear

accident

cipal hydrolysis

reduce the release of 1311 to the

establishing

by converting

Similarly,

ionic forms, iodate

(-I).

Although

matrix

of iodine hydrolysis

extensively

individual

studied

under ambient

the key disproportionation

sequence

shown below]

only one investigation

ments

that attempts

involving

of iodine hydrolysis

particularly

at low temperatures

and low pH values where the rates are slow.

Although

this aspect will not be addressed

kinetics

program

has been completed

In formulating
following

two experi-

the temperature

assumptions

based on various

lead to widely dif-

fering values for the equilibrium

values differ

with

in

to measure

the equilibrium

reactions

these

at our laboratory.
mode13,

the

were considered:

Turner2 demonstrated

to estimate

high temperatures

(3) in the

for the prin-

is essential

for iodine behavior.

here, an experimental

conditions,

[equation

of this reaction

thermodynamic

have been

has been neglected

being reportedI.

dependence

reactions

within the

equilibrium

the kinetics

are important,

(tV) and iodide

reactions

in

an exact knowledge

parameters

a model

with organic

perturb the hydrolysis

setting,

of the thermodynamic

stantially

volatile

redox and photochemical

as well as interaction

atmosphere

them to the non-

radiolysis,

constant

at

(e.g., at 150C the predicted

by 16 orders

of magnitude).

I2 t I- t 13-

(I)

12 t H20 * HOI + I- + H+

(2)

312 t 3H20 $ 103- + 51- + 6H+

(3)

HOI $ 01- + H+

(4)

HI03 $ IO3- + H+

(5)

H20I+ $ HOI t H+

(6)

I2 t H20 $ 120H- + H+

(7)

*Research sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences,
U.S. Department of Energy under contract DE-AC05-840R21400
with the Martin Marietta Energy
Systems, Inc.
+On leave from the Department

of Chemistry,

0022-3115/85/$03.3OC
Elsevier Science Publishers
(North-Holland
Physics Publishing Division)

Carleton

B.V.

College,

Northfield,

MN

55057

USA.

281

D.A. Palmer et al. / The hydrolysis of iodine

(8)

expression

Hz0 t OH- + H+

(9)

charge

12(vapor)

( 10)

equation,

120H-

+ H+

$ 1202-

* 12laqueous)

the heat capacity

It should be noted that in our initial mode13,

ture data,
I202-

species

of the total

conditions

pertinent

to nuclear

However,

150C.

the species

are retained

results

origin

in the model

to

for the

(l), (3) and (5) will be

the temperature
equilibrium

The combined

The heats of reaction

(8) are unknown
constants

pertaining

and form of the expressions

spanning

sce-

pH values

in this paper, a brief account

remaining

for equations

and therefore

were fixed at their 25'C values,

The dissociation

constant

taken from Marshall

data4-8

is needed.

for equation

(2),

where Dw represents
calculatedI

the density

as follows:

D, = 1.00017 - 2.36582 x 10-5t - 4.77122

x lo-9t3

- 44.764 + 0.070692T

the temperature

in degrees

The distribution
ween the aqueous

to which the equilibrium

constant

measured

(4) was modeled

expression

is assigned.

after the tem-

for the acid dissociation

of HOBr9, but adjusted

value of K4 for

in 'C.

coefficient

HOI at 25'C.lO The equilibrium

for this equation

by numerous

experimentalists.7315

results of these two studies7115

The

can be best

fit by the equations:

log KIO = 4220.5/T

is as follows:

- 19.991 + 0.02583T

(t < 112OC)

log KIO = 5615.4/T

- 2.0468 x 106/T2 - 526.75

- 25.179 + 0.02990T

(t > 112C)

As HOI has not been detected

Data are available8*II
for equation

for iodine bet-

and vapor phases has been

to give the measured

log K4 = 29688/T + 81.840 In T - 0.089649T

peratures

of water and is

range of 0 to 56'C, were

refers to the reaction

dependence

+ 2.2362 x 105/T2

+ 8.5641 x 105/T2) log D,

Kelvin and the subscript

perature

i.e.,

of the

where t is the temperature

Equation

Kg, was

- 3.984 x 107/T3 + (13.957 -1262.3/T

x lo-'%2 t 8.27411

T represents

for water,

and FranckI3,

log Kg = -4.098 - 3245.5/T

of the

fitted by the equation,

where

(7) and

the equilibrium

1.4 x lo-10 and 0.045, respectively.1

used to

dependencies

constants

a temperature

In K2 = -1392.9/T

on

discussion.

As new experimental

for equations

describe

in the ensuing

from 25 to

the equilibria

sake of completeness.

presented

accident

iodine and iodide

from 5 to 10, and temperatures

should be

log K6 = -2.92/T + 8.27

under the

of 10-3 to 10-7 gatom/kg,

molalities

change

(i.e.,

iodine present)

narios, -viz. initial

the

litera-

such as H103, H201+ and

were found to be insignificant

<O.Ol%

because

This point will be elaborated

minimal12.

which was based solely on the available

However,

must be used.

is the same on both sides of this

at only two tem-

(6) and hence a linear

in the vapor phase

as yet, only lower limits can be suggested

its distribution

22q.16

coefficient

(e.g., 104 at

for

282

2.

D.A. Palmer et al. / The hydrol.vsis of iodine

EXPERIMENTAL

2.2 Spectrophotometric

2.1 EMF Measurements

The triiodide

The cell used to determine

constant

for equation

the equilibrium

(3) can be represented

(I), was also studied

as

follows:

over the temperature

44.7'C.l*

The wavelengths

maintained

HC104(Wt2),

molality

KIoj(mRl) ,I2(mR)I Pt

equilibrium,

of the equipment

given elsewhere.17

and procedure

Essentially

are

the cell con-

sisted of two concentric

compartments,

each

containing

shown above.

Three

the solutions

experiments

were carried

out with

I2

of simply

HI and HIO3, respectively.

strengths

of these solutions,

were matched

as closely

The iodine molality

was varied

from 10-3 to 0.02 m,

the liquid junction

liquid junction
plug.

Platinum

potential.

consisted

cuit with the electrode

completed

the cir-

in the iodate solution

being coated with platinum

black.

tions were stirred magnetically

The solu-

throughout

The cell was initially

experiment.

NaC104

of a porous glass

electrodes

the

The key to this method

the equilibration
quired

the two solutions

of the I2/IO3-

plete within

24 hrs at 2OO'C.
as indicated

tial reading,
solutions:
determined
absorption
cm-I);18

maximum

by potentiostatic

titration
Twenty-two

Upon attaining
poten-

from both
mR,

Was

using the

experiments

the details

described

elsewhere.lg

indicated

that some oxidation

and the proton

by

NaOH solutions.
were carried

of which are

Experiments

at 100C

of Tl(1) to

Tl( III)

by iodate had occurred

imposed

an upper limit on the temperature

that could be effectively

and hence this

range

investigated.

AND DISCUSSION

ments

conditions

out over

range 3.8 to 209.O"C.

in the emf experi-

imposed a number of constraints

Firstly,

the coexistence

iodine and iodide ions at millimolal

within the cell resulted
substantial

amounts

on

data pertaining

to
of

levels

in the formation

of triiodide

order to calculate

the molalities

iodide and iodine,

a knowledge

dynamics

of I3- formation

reaction

has been well studied

ion.

temperatures
information
analyses

reliable

of the thermoThis

in the past,20
range such

in the ACp (reported

extrapolation

impossible.
is provided

directly

at

to higher

Fortunately,

of the solutions

in

of free

values vary from -263 to +97 J K-l mol-1

25'C) makes

of

Thus,

is necessary.

but only over a narrow temperature

that the large uncertainty

were measured

mL2 and mR2, were determined

the temperature

coulometry,

(3).

iodine, mL, iodate, mRI,

with standard

The solutions

and iodate by poten-

tiostatic

equation

at 460 nm (E = 730.9 M-I

coulometry;

for thallium

re-

COUPle,

COnCentratiOn,

and iodide, mLI, molalities

molalities,

range 2.2 to 75.O"C.

were analyzed

as well as

by a constant

by spectrophotometry

the total

temperature

the equilibrium

samples were withdrawn

the iodine

from the

of TlIO3 in 0.1 m

(10s4 m HC104) and 0.1 m HC104 over the

treating

up to five days at 25"C, but was com-

equilibrium,

for iodic

(5), was determined

The operating

was to allow the

This process,

via the gas phase.

constant

in solubility

3. RESULTS

between

within this range

purged with

argon and kept lighttight.

iodine to distribute

acid, equation

The ionic

The actual

with

2.3 Solubility

difference

<O.l m,

was

at each temperature.

The acid dissociation

to minimize

were

at 5 x 10-5 m, while the iodide

solutions

generally

as possible

range 15.3 to

investigated

at least nine measurements

Details

equation

'in situ' by spectro-

photometry

370, 350 and 288 nm.

Pt/ I2(mL) ,KI(mLI) ,HClO4(mL2)1)

Measurements

formation

this

from the

in the cell.

283

D.A. Palmer et al. / The hydrolysis of iodine

At equilibrium,

the free iodine molality

iodide

is equal to mR, the iodine

solution

molality

in the iodate solution,

partitioning

of iodine between

I- is equal to (mL1 - mI3-).

determinations

absorption

iodate and

value for K5 at

ionic activity

coefficients

for

in both the aci-

The results of the nine

dic and neutral media.

performed

over the 73C temperature

range can be represented

by the equation:

from 'in

due to 12, I3- and I-.

temperature
described

mean

experiments

of free

observations

data set, encompassing

and

Independent

of KI were obtained

situ' spectrophotometric

25Oc,23

total

becomes more Signifi-

TlI03 and HI03 were calculated

of I3- is

equal to (mL - mR) and the modality

of the observed

ion molalities

Using the reported

cant.

the two SO~U-

Hence, the molality

correction
hydrogen

due to the

tions which are at the same temperature

ionic strength.

in the

log K5 = -657.45/T

of the

+ 21.589 - 8.158 log T

The complete

21 experiments

range 3.8 to 209.0C,18

over the
can best be

by the equation:

At 25'C, the molal thermodynamic

are, K5 = 0.157, AH5 = -7.7

parameters

kJ mol-l,

f 0.3

f 1.3 J ~-1 mol-I, and ACp,5

As5 = -41.0

-68 * 22 J K-I mol-I I9 (c.f. AH5 = -2.8

ACp,5 = -34 f 8 J ~-1 mol-I)2I.
is the form used to describe

perature

dependence

associated

quantities

with these parameters

10, AHlo = -17.0

(5) was written

are KI = 690 f.

log K5 = 3263.8/T

+ 2.2633 + log Kg

0.3 J K-l mol-l, and "Cp,Io = -21 f 8 J K-I

which

zero for this reaction

correct

for the degree

arose from the need to

of association

acid at the relatively

high acidity

solutions

in the emf experiments,

generally

0.01 to 0.10 m.

calorimetric

lity measurements
provided

for the association

temperatures
temperature
tiostatic

range, the precision

coulometry,

work inherent
solubility

of HI03, a new study was

from 2.2 to 75.0C.1g

lyze accurately

advantages

of poten-

studies.

Accuracy

temperature

in estimating

is particularly

and therefore

K5

the

deals with estimating

potential

in the cell.

by the Henderson

The maximum

by this treatment

correction

invoked

was 3.8 mV, with the average

being less than 1 mV.

is limited by the abi-

lity to predict the activity

the species

mental

involved

dependencies

of a wide variety

of ions, the

coefficients

can best

from the revised Davies equation.25

Based on iodine solubility

NaC104 media

of
expres-

and based on the temperature

ionic activity

be estimated

of aqueous

coefficients

in the equilibrium

In the absence of relevant experi-

values,

individual

important

weaker with

equation.23324

sion for K3.

to ana-

over the previous

iodic acid becomes

increasing

The wider

and the ability

for other acids.

The final constraint

of TlI03 at

for both Tl+ and IO3- give this

at high temperatures
because

quantities

that ACT is

and that ACp,50 =

vious results obtained

This was approximated

at 25"C2I and solubi-

based on the solubility

to assuming

This is in keeping with all the pre-

ACp,9O*

the liquid junction

previous

thermodynamic

is equivalent

The third constraint

of AgI03 from 25 to 35"~,22

the necessary

undertaken

of iodic

of the

viz.

Although

measurements

in its

mol-I.18
The second constraint

in

at 25'C

kJ mol-I, Aslo = -0.6

f 0.6

However,

basic form,

of KI in the new model.

The molal thermodynamic

equation

the model,

the tem-

=
f 0.5

J K-I mol-I, and

kJ mol-I, AS5O = -24.7

log KI = 555.0/T + 7.355 - 2.575 log T

which

measurements

at 25'C, the activity

iodine was set at unity.

in

coefficient

D.A. Palmer et al. / The ~,~~dr~~ysis

ofiodine

284

The final calculated

l/T are shown in Figure

values of log Kg vs.

in the ionic strength.

1.

this form are shown in Figure 2 where the

The smooth

line is

The data expressed

smooth curve can be represented

in

by the

equation:

log K11 =

50

-6578.8/T

tf3mpex-a~ C
sJo
25

200

$45

+ 248.25 - 76.431 log T

v
40
36

d
3

35
2.0

2.5

35

1c13/TLm

FIGURE

30

Plot of the logarithm of the molal equilibrium

constant, K3, vs. l/T.

the result of a least-squares

according

2.0

fit of the data

Plot of the logarithm

constant,

molal thermodynamic

at 25C were derived,17

+ 0.22, AH3o = 272.6

log K3 =

= -1802

agreement

value obtained

with the interpolated

by Lundberg

et al.1 of -45.01.

Again, this reaction can be formulated

terms of anions

The results of combining

into the previous

The value of log K3 at 25C is

in approximate

in

(i.e. in its basic form) as

illustrated

in Figures

the upper and expected

many nuclear
ciation

accident

was calculated

that these amounts

(11)

the anionic
equation.
should

charges

term by balancing

on both sides of the

Note that the reaction

also be far less influenced

in this form
by changes

3 and 4.

levels,

are
The molalities

of molecular

The spe-

iodine were

temperature

0 and 11 and allowed

temperature

value.

The main

are, firstly

destabilizes

at

to hydro-

that

I2 with

respect to IO3- and I- at a given pH as dictated by equation

the initial

(3).

in

in each case assuming

of these diagrams

increasing

respectively,

scenarios.

lyze to its final equilibrium

features

to reduce the heat capacity

these new equations

model3

at the appropriate

any pH between

312 + 60H- $ 103- + 51- + 3H20

computer

of 12 of 10-4 to 10-6 were chosen to represent

introduced

follows,

is the one used in the spe-

ciation model.

+ 2.8 kJ mol-1,

As3 = 16 d 9 J ~-1 mof -1, and Acp,3

41 J K-1 mol-l.

of the molal equilibrium

K11, vs. l/T.

The later equation

-46.93

+ 631.24 - 216.73 log T

from which the following

quantities

33

FIGURE

to the equation,

log K3 = -42304/T

2.5

Secondly,

iodine concentration

decreasing
has the same

28.5

D.A. Palmer et al. / The hydrolysis of iodine

Thirdly,

effect.

decreasing

HOI to substantial
be remembered
measured

increasing

temperature

and

molalit ies both tend to stabilize

levels at lower pH.

that the HOI equilibria

at lower temperatures

It must
were only

and hence above

60C these results are based on extrapolation.

.-.-.-.-.-.-._*

-5

-B

-7

--R

FIGURE 4
Speciation diagrams at initial iodine molalities of 10m6 gatom/kg as a function of temperature and PH.

FIGURE 3
Speciation diagrams at initial iodine molalities of 10m4 gatom/kg as a function of temperature and pH.

286

4.

D.A. Palmer et al. / The hydrolysis of iodine

CONCLUSIONS

13.

W.L. Marshall and E.U. Franck, Water and

Steam, eds. J. Straub and K. Scheffler
(Pergamon Press, N.Y., 1980) p. 506.

14.

N.E. Dorsey, Properties of Ordinary Water

Substance in all its Phases (Reinhold
Publishing Corp., N.Y., 1940) p. 583.

15.

L.F. Parsly, Design Conditions of Reactor

Containment-Part
IV. Calculation of
Iodine-Water Partition Coefficients, ORNL
Report; TM-2412 (1970).

16.

L.M. Toth, K.D. Pannell and O.L. Kirkland,

The Chemical Behavior of Iodine in Aqueous
Solution up to 15O'C.
I. An Experimental
Study of Nonredox Conditions, ORNL Report,
TM-8664 (1984).

scenarios.

17.

D.A. Palmer, R.W. Ramette and R.E. Mesmer,

J. Solution Chem. (in press).

REFERENCES

18.

D.A. Palmer, R.W. Ramette and R.E. Mesmer,

J. Solution Chem. (in press).

19.

R.W. Ramette and D.A. Palmer, J. Solution

Chem. (in press).

20.

See twelve
18.

21.

E.M. Woolley, J.O. Hill, U.K. Hannan and

L.G. Hepler, J. Solution Chem. 7 (1978)
385.

22.

N.C.C. Li and Y.-T. Lo, J. Pm. Chem. SOC.

63 (1941) 397.

23.

P. Henderson,

Z. Phys. Chem. 59 (1907)

24.

P. Henderson,

Z. Phys. Chem. 63 (1908) 325.

25.

C.W. Davies, Ion Association

London, 1962) p. 41.

The principal

equilibrium

iodine has been established

function

of temperature

computer

model

these new data.

ten aqueous

chemistry

in the absence

has been adapted

temperature

of

of added

to include

The concentration

iodine species,

iodine,

as a

for the first time.

levels of

as well as vapor

phase iodine, can be estimated

initial

aqueous

quantitatively

for the aqueous

iodine at equilibrium
redox partners

involving

as a function

of

iodide and iodate molalities,

and pH.

pass those anticipated

These conditions
in nuclear

encom-

accident

1.

W.O. Lundberg, C.S. Vestling and

J.E. Ahlberg, J. Am. Chem. Sot. 59 (1937)
264.

2.

D.J. Turner, Water Chemistry of Nuclear

Reactor Systems, (BNES, London, 1978) pp.
489-533.

3.

D.A. Palmer and M.H. Lietzke,

Acta 31 (1982) 37.

4.

W.C. Bray and E.L. Connolly,

Sot. 33 (1911) 1485.

5.

G. Horiguchi and H. Hagisawa, Bull.

Phys. Chem. Res. 22 (1943) 661.

6.

T.L. Allen and R.M. Keefer,

sot. 77 (1955) 2957.

7.

W. Eguchi, N. Adachi and M. Yoneda, J.

Chem. Eng . , Japan 6 (1973) 389.

8.

J.D. Burger and H.A. Liebhafsky,

Chem. 45 (1973) 600.

9.

C.M. Kelley and H.V. Tartar,

Sot. 78 (1956) 5752.

Radiochim.

J. Am. Chem.

J. Am. Chem.

Anal.

J. Pm. Chem.

10. Y.-T. Chia, Ph.D. Thesis, University

California, Berkeley (1958).
11. R.P. Bell and E. Gelles,
(1951) 2734.

Inst.

of

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12. C.F. Baes, Jr. and R.E. Mesmer,

281 (1981) 935.

Am. J. SCi.

references

cited in Reference

118.

(Butterworths,