ARSENIC(III) AND ANTIMONY(III) AQUEOUS CHEMISTRY

Research Collection

Doctoral Thesis

UV spectrophotometric studies of arsenic(III) and antimony(III) aqueous chemistry from 25 to 300°C Author(s): Iakovleva, Valentina P. Publication Date: 2003 Permanent Link: https://doi.org/10.3929/ethz-a-004685440

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ETH Library

DISS. ETH No. 15343

UV SPECTROPHOTOMETRIC STUDIES OF AND

ANTIMONY(III) AQUEOUS

ARSENIC(III)

CHEMISTRY

FROM 25 TO 300°C.

A dissertation submitted to the

SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH for the

of

degree

Doctor of Science

presented by VALENTINA P. IAKOVLEVA

Dipl. Geologist-Geochemist,

Moscow State

University,

Russia

born 19.05.1975

citizen of

Russian Federation

accepted

on

the recommendation of

and

Pétrographie,

Prof. Dr. T. M. Seward

Inst.

Mineralogy

Prof. Dr. C. A. Heinrich

Inst.

Isotope Geochemistry,

Prof. Dr. S. A. Wood

University of Idaho, Moscow, USA

2003

ETH Zürich

ETH Zürich

examiner co-examiner co-examiner

The

cover

illustrations show: absorbance spectra

arsenic and

antimony sulphide deposition

Pool, Waiotapu Geothermal System, New

on

oîAs(III) sulphide containing solutions;

siliceous

Zealand.

algal

stromatolites at

Champagne

To my

grandfathers

General A. M. Volkov

Professor

N. P. Zakaznov

Abstract

The aim of this

dynamic and

study

has been to

provide

a

data which define the ionisation of

HzSbO^)

addition,

the

and

p-nitrophenol and

stability

able to determine the a

new

experimental set-up

measurements in

of the

was

The main

uv-vis

stoichiometry

designed

and its

developed

region

validity

of

(i.e. HAsÖ2

which

our

In

species have also

method used in this

However,

in order to be

of the thioarsenite aqueous

species,

and constructed which facilitated accurate

and

solutions.

A mathematical treatment

successfully applied.

deprotonated equivalent

the visible and ultraviolet test and confirm the

was

experimental

spectroscopy.

hydrogen sulphide containing

experimental data

p-nitrophenol

and

stability

based thermo¬

and antimonous acids

of the thioarsenite aqueous

stoichiometry

high temperature flow-through

is

arsenous

experimentally

from 25 to 300°C at saturated vapour pressures.

been determined at ambient temperature.

study

reliable set of

Dilute solutions of

exhibit well defined spectra

comprise

a

throughout

simple, ideal system with which

spectrophotometric methodology

to

and mathematical

data treatment.

The ultraviolet spectra of dilute

antimony and

arsenic aqueous solutions have been

sured from 25 to 300°C at the saturated vapour pressure.

stability

constants

were

obtained for the

HAs02(aq) for which 25 to

pKi (arsenous acid)

9.

species and stability

constant

solutions, the reduced sulphur concentrations

four times greater that that of arsenic and hence all

acid

arsenous

was

species reacted

to

thioarsenite.

The thioarsenious

sulphide species

and

fluids,

K\, for the thioarsenous acid

sulphur hydrothermal

As02 the

,

,

were

in dilute aqueous solutions at ambient

isation constant,

In low

species, H3AsS3 and H2AsS3

was

found to be the dominant

temperature and pressure. The ion¬

obtained,

fluids in the Earth's crust, the

(i.e. p.rYi=11.14±0.04).

and

simple

species will be the dominant arsenic species. However,

fully protonated H3AsS3 species

solutions, the

-As2 CO

oo oo CO CO

Ö

Ö co o 4^ Cn

O

I—i

O oo 4^

I—»

CD

1—i

1—»

O O

Ö

O

cn O

cn

ö

CO co o -a

p Ö

1—"

-J Oi

to

O

4^

1—»

o o

p Ö

to o

o

CD 00

-a

o

1—1

o

—>

1—i

O o

Ö

O

i—»

cn

-4

Ö

4^

O CO

4^

Ö

O

-q o Cn

to

o

CO

1—1

o o

p ö

i—»

to

to

Cn CO

i—»

oo -

"/.STABILITY CONSTANT EVALUATION /As-Na system y,

% 1.

Model

"/. 2.

Constants

used

general script"

"in

description:

densities):

(water dissociation constant,

°/."water_constants_densities" "/.

3.

Parameters

(total concentrations,

density correction)

Absorbance,

°/,"in general script" % 4.

calculation:

coefficients

Activities

"/." [I]=ion_str(C104)

"

;

"Debye_Huckel2" ;Pitzer_Agamma_derivD_H;

°/,"activity_calculation" y,5.

calculation

concentrations

Equilibrium

at

known Kt-d:

a

"/."balance. ." % 6.

Molar

constrained

"/, 7. "/„

calculation,

theorethical

°/,"object_absorbance" Minimisation

8.

"eps=nonnegative_ls(Abs,c,m);"

optimisation:

Absorbance

(5,6,7

of this

"/, 9.

Figures:

°/,10.

Uncertainty

"/.11.

Workspace saving:

using Lagrange multiplier,

calculation

absorptivity

in this "in

sum:

sum

of

separate

squares Aobs-Acalc:

program)

general script"

"figures" calculation "in

using

propagation:

Gaussian

general script,

save..."

in

"uncertainty"

the

name

"/, which system and temperature

*/.-

-----------------------

7.1.

HA=H+

+

A-;

k=H*A/HA; pH

clear all;close

varied

by

NaOH addition

all

water_constants_densities

run

lgkw=lgkw25 ; "/. !

change

d=d25; "/.density

!

°/,3.

Parameters

when

change

temperature is changed

when


:

load

E:\matlab_files\Data\data_25_300_As_NaOH.mat

load

E:\As_OH_system\AS_final_data\eps_OH.mat"/.

"/.corrected for density,

but

kk=[k_order(l :8)] ;°/,which ll=f ind(lambda==250)

:

not

for

chemical

OH molar

path length solutions

1 :f ind(lambda==196)

to

use

;°/.which wavelength interval

As=As(kk)'; Na=Na(kk)'; Abs=A(ll,kk)'/d;

eps_OH=ka(ll) ;"/, ! change

when

absorptivity


114

APPENDIX C

COMPUTATIONAL PROGRAMS

"/.run activity_calculation; "/.effect

on

stability

Ion

constant

strength is

is

less

10~-3,

then

negligible

n=length(As); m=3;°/,number

of

absorbing species

options=optimset('Display','iter','TolX',le-9); if

1

lgx_min

=

fminbnd(@obj ect_abs_As_Na,-10,-7,options,lgkw,As,Na,Abs,eps_0H);

end

[F_min,eps,C_abs,pH,oh]=obj ect_abs_As_Na(lgx_min,lgkw,As,Na,Abs,eps_0H); correct eps for path length of the cell run Figures_As_Na "/.important to confedence level run uncertanties_As_Na °/,pm-is cd

E:\matlab_files\Results result_25_As_NaOH lgx_min pm F_min eps C_abs pH kk 11 lambda As Na Abs

save

"/,

!

change

the

name

when

temperature is changed! ! ! !

115

!

APPENDIX C.


"/.SCRIPT FOR PLOTTING FIGURES:

figure°/.l plot(lambda(11),Abs) xlabelCWavelength / nm') ylabel('Absorbance') title(['Spectra of arsenic containing solutions;

Solutions:

'

num2str(kk)])

figure#2 [T,P] orthog_plot(Abs,3,lambda(ll)); =

title(['Orthogonal

vectors,

number

of

species'])

figure°/,3 plot(lambda(ll),[eps; eps_0H]) legend('undissociated species','deprotonated species') xlabelCWavelength / nm') ylabel('/epsilon') title('Molar absorptivities of HAsO_2 and As0_2"-')

figure'/.4 plot(lambda(ll), C_abs'*eps+oh'*eps_OH,'o') hold on; plot(lambda(ll), Abs) xlabeK'Wavelength / nm') ylabel('Absorbance') title(['Comparison between calculated (o) and observed (line) absorbance; resn='num2str(F_min)]) lgx_l=' num2str(lgx_min) ';

f igure°/,5

path=1.8 "/.for example "/. plot (lambda(ll), [eps]/path)

legend('HAsO_2','As0_2"-') xlabelC Wavelength / nm')

ylabel('/epsilon') title('Molar absorptivities of HAsO_2 and As0_2~- corrected for the path

length

of

the

cell')

116

APPENDIX C.

"/.SCRIPT:


WATER CONSTANTS

AND

DENSITIES:

lgkw25=-14;

lgkw50=-13.276; "/. Igkw75 */. Igkw80 7. Igkw90

lgkwl00=-12.266 lgkwl50=-11.644

lgkw200=-l1.302 lgkw250=-11.196

lgkw300=-l1.301 d25=l; d50=l;

dl00=0.9625; dl50=0.9217; d200=0.8703; d250=0.8058; d300=0.7153:

117

APPENDIX C.

"/.FUNCTION:

ORTHOGONALISATION

[T,P]

function

=

OF

MATRIX,

orthog_plot(A,n,lambda);

"/,

orthogonal izat ion [Y,I]=sort(sum(A)) ;

tmp=size(I) ; startvector=I(l,tmp(2))

;

I

=

tl

=

A(:.startvector);

t2

=

0;

for

l:n

sum(abs(t2-tl))

while t2

pi pi

>

=

tl;

=

t2'*A/(t2'*t2);

=

pl/sqrt(pl*(pl'));

tl

=

if

I

==

P

=

T

=

0.00001

A*pl';

end

1

pi; tl;

else P

=

T

=

[P; pi]; [T, tl];

end A

end

=

A-tl*pl;

figure plot(lambda, P)

118


written

by

0.

Suleimenov

APPENDIX C

"/.FUNCTION

function


OBJECTIVE

:

[F,eps,C_abs,pH,oh]=obj ect_abs_As_Na(lgx,lgkw,As,Na,Abs,eps_0H);

n=length(As); for

j=l:n

[h(j),oh(j),haso2(j),aso2(j)]=balance_As_Na(lgx,lgkw,As(j),Na(j)); end

C_abs=[haso2;aso2]; pH=-logl0(h); Abs_OHcorr=Abs-oh.'*eps_0H;

eps=nonnegative_ls(Abs_0Hcorr,C_abs,2); A_cal=C_abs.'*eps; F=sum(sum((Abs-A_cal).~2));

119

APPENDIX C.

"/.FUNCTION:

function

NONNEGATIVE LEAST


SQUARE FIT OF ABSORBANCE,

eps=nonnegative_ls(Abs,c,m);

°/,m-number of absorbing species

[ml,nl]=size(Abs); [m2,n2]=size(c);

eps=zeros(m2,nl); for

j=l:nl;

eps(:,j)=inv(c*c')*c*Abs(:,j); c_new=

[]

;

index=0; for

i=l:m

eps(i,j)0

eps_new=inv(c_new*c_new')*c_new*Abs(:,j); 1=1; for

i=l:m if

(eps(i,j)>0) eps(i,j)=eps_new(l,:)

;

1=1+1; end

end end

end

120

written

by

F.

Herzog

APPENDIX C

"/.FUNCTION

function


OBJECTIVE

:

[F,eps,C_abs,pH,oh]=object_abs_As_Na(lgx,lgkw,As,Na,Abs,eps_0H);

n=length(As); for

j=l:n

[h(j),oh(j),haso2(j),aso2(j)]=balance_As_Na(lgx,lgkw,As(j),Na(j)); end

C_abs=[haso2;aso2]; pH=-logl0(h);

Abs_OHcorr=Abs-oh.'*eps_0H;

eps=nonnegative_ls(Abs_0Hcorr,C_abs,2); A_cal=C_abs.'*eps; F=sum(sum((Abs-A_cal)."2));

121

APPENDIX C.

"/.FUNCTION

SPECIATION

:

PROGRAM,

idea from 0.


Suleimenov

[h,oh,haso2,aso2]=balance_As_Na(lgx,lgkw,As,Na);

function

na=Na; astot=As;

k=10~(lgx); kw=10-(lgkw); C(l)=l;

C(2)=k+na; C(3)=-k*astot+k*na-kw; C(4)=-k*kw; a=roots(C); °/0everythink k=0;

in=l;

if

for

is

OK

i=l:3

isreal(a(i)) if

a(i)>0 & a(i)0 & haso2>0 &

aso2>0

in=i; end

k=l; end

end end

h=a(in); oh=kw/h; haso2=(astot*h+kw-h*na-h~2)/h;

aso2=-(kw-h*na-h~2)/h; if

(k==0)

error('No real

roots

between 0

and

astot!!!')

end

122


APPENDIX C.

"/.FUNCTION

SPECIATION PROGRAM WITH NaOH ASSOCIATION

:

function[h, oh,haso2,

aso2,

na,

naoh]=balance_As_Na_assoc(lgk,lgkw,As,NA,

lgkam); AS=As;

NA=Na;

kw=10~(lgkw); kl=10~(lgk); kam=10~(lgkam); c(l)=kw*kanT2-kl*kam; c(2)=kw~2*kam'3+kl-kl*kam"2*kw-kw*kam-3*kw*kam"2*NA+2*kl*kam*NA-kl*AS*kam; c(3)=-3*kw~2*kam'N3*NA+kl*AS*kam*NA+3*kw*kam''2*NA~2+kw*kam*NA+2*kl*kw*kam"2*NA -kl*NA~2*kam;

c(4)=-kw*kam'2*NA"3+3*kw~2*kam'3*NA~2-kl*kw*kam~2*NA"2; c(5)=-kw~2*kam~3*NA"3;

g=roots(c); kl=0; t=l; for u=l:4 if

isreal(g(u)) if

g(u)>0

g(u)0

if

phtal=a(i); hp

=

P-phtal;

-Ka*(-P+phtal)/phtal; h2aso3 -(-kw*phtal~2+Ka*K*phtal*P-Ka*K*phtal~2+Ka*NA*phtal*Ph

=

=

Ka*NA*phtal"2+Ka"2*P~2-2*Ka"2*P*phtal+Ka"2*phtal"2-Ka*P"2*phtal+ Ka*phtal"3)/pht al/Ka/(-P+pht al); oh=kw/h;

(-AS*Ka*phtal*P+AS*Ka*phtal~2-kw*phtal~2+Ka*K*phtal*PKa*K*phtal"2+Ka*NA*phtal*P-Ka*NA*phtal"2+Ka'2*P"2-2*Ka'*2*P*phtal+ Ka~2*phtal~2-Ka*P~2*phtal+Ka*phtal~3)/phtal/Ka/(-P+phtal) ;

h3aso3

if

=

&

hp>0

h2aso3>0 & h3aso3>0 & h>0

t=i; end; end

end end

phtal=a(t); hp h

=

=

P-phtal;

-Ka*(-P+phtal)/phtal;

h2aso3

=

-(-kw*phtal"2+Ka*K*phtal*P-Ka*K*phtal~2+Ka*NA*phtal*P133

APPENDIX C.


Ka*NA*phtal~2+Ka~2*P~2-2*Ka~2*P*phtal+Ka~2*phtal~2-Ka*P~2*phtal+ Ka*phtal~ 3)/pht al/Ka/(-P+pht al); oh=kw/h;

(-AS*Ka*phtal*P+AS*Ka*phtal"2-kw*phtal~2+Ka*K*phtal*PKa*K*phtal~2+Ka*NA*phtal*P-Ka*NA*phtal~2+Ka~2*P~2-2*Ka~2*P*phtal+

h3aso3

=

Ka"2*phtal~2-Ka*P"2*phtal+Ka*phtal"3)/phtal/Ka/(-P+phtal);

134

APPENDIX C

"/.FUNCTION

function

:


SPECIATION AT EACH POINT OF TITRATION

[Q]=matal(pkw, pkl, pKa.NAl, ASl, Kl, Pl,Vn,Vd);

°/,Vn=solution volume

on

titration

the

start

[0.01:0.5:10]

in ml example [NA, AS, K, P]=OHdelutKHP(NAl, ASl, Kl, PI, Vn, Vd);

°/,Vd=added

solution volume

[h, oh, h2aso3, h3aso3, hp, phtal]=KHPtitr(pkw, pkl, pKa, NA(1), K(l), P(l), AS(1)); Q=[h

oh

h2aso3

h3aso3

hp

phtal];

y=size(Vd); for

i=2:y [h, oh, h2aso3, h3aso3, hp, phtal]=KHPtitr(pkw, pkl, pKa, NA(i), K(i), P(i), AS(i)); Q=[Q;h

oh h2aso3 h3aso3

hp phtal];

end

135

APPENDIX C.

"/.FUNCTION

:


OBJECT FUNCTION FOR TITRATION DATA TREATMENT

[G]=perl(NAl, pkw, pkl, pKa.ASl, Kl, Pl.Vn.Vd, X); [Q]=matal(pkw, pkl, pKa.NAl, ASl, Kl, Pl,Vn,Vd); W=diff(-loglO(Q(:, 1))); function

a=size(Vd'); f=a(:, 2)-l; v=size(Vd(l:f)); u=size(W); S=[Vd(l:f) W];

s=size(S);

[y, m]=min(S); x=S(m(2),

1);

G=(X-x)~2;

"/.primer resheniya v \from Cary5\matlab26_05_99_calk.txt. °/.pKa konstanta dlya KHP, X-min v diriviate exp, Vn-m sol °/.Vd,

skol'ko

dobavlyala, K-C(K).

.

.

136

s

As,


APPENDIX C.

"/.FUNCTION function

:

TO

CALCULATE DILUTED CONCENTRATIONS

[NA, AS, K, P]=OHdelutKHP(NAl, ASl, Kl, PI, Vn, Vd);

°/,Vn=solution volume

on

the

titration

°/0Vd=added solution volume example

start

[0.01:0.5:10]

AS=AS1*Vn/(Vn+Vd(1));

NA=NAl*Vn/(Vn+Vd(l));

P=Pl*Vd(l)/(Vn+Vd(l)); K=Kl*Vd(l)/(Vn+Vd(l));

d=size(Vd); i=2:d

for

FOR TITRATION

as=ASl*Vn/(Vn+Vd(i)); na=NAl*Vn/(Vn+Vd(i));

p=Pl*Vd(i)/(Vn+Vd(i)); k=Kl*Vd(i)/(Vn+Vd(i)); AS=[AS ; as];

NA=[NA;na];

P=[P;p]; K=[K;k]; end

137

in ml

APPENDIX C.

138


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CURRICULUM VITAE

Valentina P. Zakaznova-Iakovleva

Name: Date

of Birth:

May 19, Russian

Nationality: Education:

1975

1982-1992:

Moskovskaya Gymnasia

(Primary 1992-1997:

Diploma

and

1998-2003:

(M.Sc.)

in

Geology

Russia

and

Geochemistry

University, Russia

Ph.D. student in Institute für

Yugo-Zapade

Secondary schools), Moscow,

with honor

Moscow State

na

Geochemistry

Mineralogy

und

Petrography,

ETH-Zentrum

Zürich, Switzerland Awards:

Languages:

1996:

"Academician D.S. Korzhunskii

Stipend",

Russia

1997:

"Academician D.S. Korzhunskii

Stipend",

Russia

Russian

(mother tongue), English

and German

Acknowledgments

I would like to thank many

the

possibility

Oleg

group.

to do

a

people

set-up experiments and

doing

me

at ETH

version and

me

hope;

a

personal

of fun times

together.

We

friends,

kept

Hönggerberg;

our

these years.

during

supervision within

Dr.

Kissner for

a

friends,

Thank to Florian for all his

without your

patience, support and advice

thanks to my Parents for the love and energy

in both

they

how to

spectrometric my

"first"

alive;

I have realised that

help;

personal

arenas.

Finally,

mass

me

for great company and lots

for their support in difficult moments.

possible

motivated research

correcting

traditions and habits very much

my Ph.D. would not have been

Terry Seward for

teaching

doing

Trudi Semeniuk for

note I would like to thank my Russian

Thanks to all my

finishing

me

ab intio calculations and for

to write programs;

measurements for

On

helped

doctoral thesis under his

Suleimenov for

giving

who

gave

me.

and scientific