DISS. ETH No. 15343. UV SPECTROPHOTOMETRIC STUDIES OF ARSENIC(III)
. AND ANTIMONY(III) AQUEOUS CHEMISTRY. FROM 25 TO 300°C.
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
temperature is changed
:
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
temperature is changed
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.
COMPUTATIONAL PROGRAMS
"/.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:
COMPUTATIONAL PROGRAMS
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
COMPUTATIONAL PROGRAMS
written
by
0.
Suleimenov
APPENDIX C
"/.FUNCTION
function
COMPUTATIONAL PROGRAMS
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
COMPUTATIONAL PROGRAMS
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
COMPUTATIONAL PROGRAMS
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.
COMPUTATIONAL PROGRAMS
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
COMPUTATIONAL PROGRAMS
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.
COMPUTATIONAL PROGRAMS
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
:
COMPUTATIONAL PROGRAMS
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
:
COMPUTATIONAL PROGRAMS
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,
COMPUTATIONAL PROGRAMS
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
COMPUTATIONAL PROGRAMS
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.12. Dielectric prop¬
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L. E.
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(1992)
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The
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M., Belzile
Garrett
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Reactivity.
D.C. Heath and
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N. and Chen Y.
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A.B., Holmes O
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Geochim. Cos-
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Arsenic speciation by
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(1940)
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Haar
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Pokrovski G.
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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