volume xxxv - journal of chemical technology and
TRANSCRIPT
VOLUME 43 2008 ISSUE 1
www.uctm.edu ISSN 1311-7629
JOURNAL OF THE UNIVERSITY OF CHEMICAL TECHNOLOGY
AND METALLURGY
SOFIA
Journal of the University of Chemical Technology and Metallurgy UCTM has been publishing the journal called Annual of the University of Chemical Technology in Bulgarian language since 1954. Thirty four volumes have been issued. It has been transformed into a Journal of the University of Chemical Technology and Metallurgy published in English since 2000 (volume 35). JUCTM is published quarterly.
Honorary Editor R. DIMITROV
Editor-in-Chief B. KOUMANOVA
University of Chemical Technology and Metallurgy,
8 Kl. Ohridski blvd., 1756 Sofia, Bulgaria Tel: (+ 359 2) 8163 302, E-mail: [email protected]
Editorial Board
ALLEN S., Queens University of Belfast, UK ANGELOVA D., UCTM, Bulgaria BORISSOVA R., UCTM, Bulgaria CARDA J., University Jaume I, Castellon, Spain CASAMATTA G., Institut National Polytechnique de Toulouse, France CHOLAKOV G., UCTM, Bulgaria DIMITROV G., UCTM, Bulgaria DISHLIEV A., UCTM, Bulgaria DISHOVSKY N., UCTM, Bulgaria FROYER G., Institut des Matériaux Jean Rouxel, Nantes, France GECHEV P., UCTM, Bulgaria
JITARU M., University “Babeş -Bolyai”, Cluj-Napoca, Romania KALTCHEVA S., UCTM, Bulgaria KASHCHIEVA E., UCTM, Bulgaria KEIL F., Hamburg University of Technology, Germany KONSTANTINOVA T., UCTM, Bulgaria KUCHARSKI M., AGH University of Science and Technology, Krakow, Poland MEHANDJIEV D., Bulgarian Academy of Sciences, Bulgaria
MEŠKO V., Sts. Cyril and Methodius University, Skopje, Macedonia MÖRL L., University “Otto-von-Guericke”, Magdeburg, Germany
NATH B., European Centre for Pollution Research, London, UK PETROV L., Bulgarian Academy of Sciences, Bulgaria STEFANOVA V., UCTM, Bulgaria STOILOVA D., Bulgarian Academy of Sciences, Bulgaria VASSILEVA S., UCTM, Bulgaria VASSILEV V., UCTM, Bulgaria VELEVA S., UCTM, Bulgaria ŽIVKOVIC Ž., University of Belgrade, Technical Faculty, Bor, Serbia
Technical secretaries: Staneva A., Georgieva S.
The annual subscription (for 4 issues) is 200 €, including postage, handling and packaging charge.
©UCTM, 2005. All rights reserved. Reproduction in part or whole without permission is strictly prohibited. Prepress and design: Staneva A.; Printing: S Print Ltd., Sofia The articles of this journal are indexed and abstracted in Chemical Abstracts and Referativnii Journal Himii (VINITI).
The abstracts and the addresses of the authors are included in the web page of the UCTM (www.uctm.edu/JUCTM 08-1/).
TABLE OF CONTENTS
PHYSICAL CHEMISTRY
This chapter contains contributions presented at the Scientific Conference with International Participation
dedicated to 60th Anniversary of the Department of Physical Chemistry, UCTM, 2007
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 5-10
THE WORLD SCIENTIFIC MARKET AND BULGARIAN SCIENTISTS
D. Pavlov
Plenary lecture presented at the Scientific Conference with International Participation
dedicated to 60th Anniversary of the Department of Physical Chemistry, UCTM, 2007
Institute of Electrochemistry and Energy Systems,
Bulgarian Academy of Sciences,
Acad. G. Bonchev str., bl. 10, Sofia 1113, Bulgaria,
E-mai: [email protected]
ABSTRACT
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WHAT DOES SCIENCE PRODUCE?
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INSTITUTIONS AND ORGANIZATIONS ACTIVEON THE WORLD SCIENTIFIC MARKET
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Which research units of the Bulgarian Academy ofSciences (BAS) and of the universities can sellknowledge on the world scientific market?
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How did the access of our Department to the worldscientific market influence our scientific production?
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Fig. 1. Growth in total number of papers published in internationaljournals and conference proceedings throughout the years.
Fig. 2. Increase of the total number of citations of our papersby foreign authors throughout the years.
Fig. 3. Number of citations of publications of the LABD byforeign authors per year.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
10
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Country Organization Contact researcher
China Shandong University Prof. Y. Guo
Finland University of Helsinki Prof. G. Sundholm
Germany TU Dresden Prof. K. Wiesener
Italy Politecnico di Torino Prof. M. Maja
Russia Institute of Electrochemistry Dr. K. Rybalka
Russia Institute “Iztochnik” Dr. A. Russin
Sweden Royal Technical University Prof. D. Simonsson
EC CMP Batteries Ltd. (UK)
S.E.A. Tudor S.A. (Spain)
Dr. I. Dyson
Dr. E. Trinidad
EC CEAC-CEA Dr. L. Torcheaux
Finland Neste Oy Dr. Passiniemi
Germany Varta Battery Mfg. Co. Dr. Gereth
Germany Maschinenfabrik Gustav Eirich Mr. P. Eirich
India AMCO Dr. R. Vishwanathan
Iran Niru Battery Mfg. Co Mr. S. Tabaatabaai
Japan JSB Co., Ltd. Dr. Tsubota
Norway Borregaard Lignotech Dr. Myrvold
Switzerland Oerlikon Dr. H. Giess
Taiwan MRL, ITRI Dr. C. Liu
USA ALABC/ILZRO Dr. R. Nelson,
Dr. P. Moseley
USA FireFly Energy, Inc Dr. E. Williams
USA Exide/GNB Technologies Dr. M. Kepros,
Dr. R. Batson
USA USA ARMY R&D Centre Dr. Henry Catherino
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11
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 11-18
EASY TEST UNIT FOR HYDROGEN ELECTROCHEMICAL ENERGY CONVERSION
E. Budevski, I. Radev, E. Slavcheva
Institute of Electrochemistry and Energy Systems,
Bulgarian Academy of Sciences,
Acad. G. Bonchev str., bl. 10, Sofia 1113, Bulgaria
ABSTRACT
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Accepted 12 December 2007
INTRODUCTION
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Fig. 1. The autonomous test cell unit. Left: cross section side view. Right: a cross section front view.
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Fig. 2. The “hydrogen version” of the EasyTest Cell.
Fig. 3. The EasyTest Cell. TE – test electrode; RRE – reagentrecovery electrode; RE – reference electrode. On the right handside an exploded view of the cell stack is given with dimensionaldetails.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
14
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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Fig. 6. HOR polarization curves on A Pt Ir test eledtrodes athydrogen pp’s varying between 0,012 and 5,52 bar. RRE: E Pt050.Gas composition: <T80RH100TP(600-125)H(0012-5,52)Ar>s.Table 1 and 2.
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REFERENCES
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2) values.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
18
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19
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 19-28
SIMULATION OF ADSORPTION AND PHASE TRANSITIONSOF GASES ON METAL SURFACES
F. J. Keil
Hamburg University of Technology,
Eissendorfer Str. 38, 21073 Hamburg, Germany,
E-mail: [email protected]
ABSTRACT
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Received 23 November 2007
Accepted 12 December 2007
INTRODUCTION
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Fig. 1. Supercell approach.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
22
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23
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
24
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Fig. 6. Logarithm of the configurational density of states lnΩ(E)against the energy per atom.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
26
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F. J. Keil
27
RESULTS FROM MONTE CARLO SIMULATIONS
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REFERENCES
"2<04::&A#A
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/> "A+:
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2 04::4
"4<5*2/;1
11
<4::'4?
"#1L Fig. 8. H/Pd(111) Monte Carlo phase diagram (--------) and LEED( ) experiments.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
28
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A. Girginov, M. Bojinov
29
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 29-36
CONDUCTION MECHANISMS IN THE(+) VALVE METAL/OXIDE FILM/ELECTROLYTE SYSTEM
A. Girginov, M. Bojinov
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
!
Received 23 November 2007
Accepted 12 December 2007
INTRODUCTION
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*+
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,
*+
E
)!
-+.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
30
"≅ / *0
"!
!!
-0.!1!2
( % "
*0
IONIC CONDUCTION
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!
3
"E!
&'!('-4.)!*-56.
Fig. 1. Ionic (Ji), electronic (J
e) and dissolution (J
dis) currents in
(+)valve metal/barrier oxide/electrolyte systems.
V
alve
Met
al
Oxi
de fi
lm
Je
Ji
Electrolyte
Anode
Jdis ,
"+E
,
&'(')
"
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+
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k T
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, -80.!
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B
B
k T
−
2Y Y
B
E E
k T
α β −
4
Fig. 2. Schematic picture of anodic alumina films: (a) barrier type anodic oxide film; (b) porous type anodic oxide film.
A. Girginov, M. Bojinov
31
9:(
:0
:β
:
%;
<4
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*-?.
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t
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MzD J t dt
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ELECTRONIC CONDUCTION
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)
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-
1/ 21
1s
s
εε
− +
3/ 20
1/ 2i B
e
k Tε E+(0. =
%5π/"F0(4=
>!
χ/"
( >+!!
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
32
(
"F('!
<!/
GG
!
#8=!
αβ
)
α!0 dN χ
/("F ?
1/ 21
1s
s
εε
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e
k TεD
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COUPLING BETWEEN OXIDE GROWTH ANDMETAL DISSOLUTION
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-5+50.
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H$H$
!
H$-55.% !
H$!
(
m 3 6VIW O mW V e••→ + + +/
!
(
423 3 3 6k
O OV H O O H•• ++ → + ++
"
63 22(3 ) (3 )dk
xWO x H W x H O+ +− + − → + − +0
!
H$ !
!
A. Girginov, M. Bojinov
33
#H$*(B
6
aqW +!
H$J
)
2' 6 ' 6 'kVW aq WW W e V+→ + +
+4
31
32
' * '
* 6 6'
kV VIW W
kVIW aq W
W W e
W W V+
→ +
→ + +5
@ !
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6'O WV V null•• + → +6
! !
0 020 ( ) , (0)
2 2
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o O M M
D DJ c L e J c e
a a
χ
= − =
E
+8
2 6o mI FJ FJ= − +
((
0E
" -5+.
( )0 / / /M F F SE EL Lφ φ= + +
+=
φK(*+!α<EE
2φ
*(B
2*(B(εε
L
(
!
( E
"2*(B
,-5+.*!
K!@K -54.
(
C
!
)
0 /0
0
0 /
0
2( ) exp (1 ) ,
6 6(0) exp (1 )
2
n F So
n F SM M
FD q LFaI c L E
a RTL
FD q LFaI c E
a RTL
αεε
αεε
= − + = − +
+?
% (
K*(B
! K
#B
B
!
, /, /
M F S MnM F S M O n O n
O
I IdqI I I Sq I S q
dt I S
− = − − = −
+D
%
( )
5'2 5 32 6*
6M
M
IJ k k
Fγ γ= = + 0/
M6M
8J *(B !
H$ H$J
!
H$!
M6M
8J
)
52 5 31 56
Md Ik k
dt F
β γ γ γ= − − 0+
631 5 32 6
**
dk k
dt
β γ γ γ= − 00
, /2 315 5 0
6M F SI
k kF
γ γ− − = 04
*315 632 0k kγ γ− = 05
*
5 6 6 1γ γ γ+ + = 06
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
34
6γ H#4
H$
<0/05
06 , /M F SI )
( ) ( ) ( )2 3132, / 6 6
31 32
61 1M F S M
Fk k kI k
k kγ γ
+= − = −
+08
MI ( )61 γ−H$ OI
6γ
3
'6 6 62 2n
O d d WOHI Fk c Fk kγ γ γ+= = = 0=
!
<+09'
6γ
H$H$
3
3
6WO
M WO
k
k kγ =
+ 0?
3
2M
M
M WO
kI
k k=
+ 0D
3
3
2WO
O
M WO
kI
k k=
+ 4/
*
"
IK
I#
1
1 1el
O M
Z R j CZ Z
ω−
= + + +
4+
=1
1
0
(1 )C E
E
αεε
− −= 40
*
! )
00
/
0
F Sn
I S EL
qj I S
εεα
ω=
+44
x
0 /
0
2 2(1 ) ,F S
o n
I B L FaI E q B
RTLα
εε
= − + =
45
B4445!
1 0 0 0,
0
2(1 )O f
I I B I SZ
E L j I S
ααω
− ∆= = − + ∆ + 46
""
(1 )
6mV
I j EFE
α ωλ−= 48
!
O
O M
I
I Iλ =
+ !
)
( )0
(1 )
6m
O MO
VC I I
FI E
α−= + 4=
,0
1O O fZ Z
j Cω= + 4?
!
*(B
<0/0+00
A. Girginov, M. Bojinov
35
*1
2 5 6, / 2 5 326M F SZ F k k kγ γ γ− = + + 4D
1, /
2 2 31 315 5 5 5 5
* *31 316 5 5 632
6M F SZ
j k k k kF
j k k k
ωβγ γ γ γ γ
ωβγ γ γ γ
−
= − − − −
= − −5/
* 31 315 5
632
k k
j k
γ γγβ ω
+=+ 5+
( ) ( )
( )1
2 315, /5
2 31 2 316
M F Sk kZ
F j k k j k k
γγ
β ω β ω
− += −
+ + + + 50
2 5, / 26 1M F SZ Fb k γ
= +
54
( )( )( )
31 2 3131
22 22 31 31 22 32 31 2 312
2 312 32 31
1
b k k k
k bj b k k b k k k b b
b k k b k
ωβ
−+
+ + + − +
!
46
1 0,
0
6(1 )M M
M f
I SI I BZ
E L j I S
ααω
− ∆= = − + ∆ + 55
!
IK)
, , /M M f M F SZ Z Z= + 56
4+404?56!
!
!!
H! !
"
9 !
-58.
CONCLUSIONS
((!
!
!
!
"
"!
(
" !
(
!!
! !
C!
!
!
( !
Acknowledgements>;
=)?.
!@*ABCD9ECC=
REFERENCES+N:% %O;
:" +D8+
0 *PK9 > Q<
B+D645++
4%&,9F,IO+D4548=
5N:O>B+D8/5D8
6N:O>B+D8+4D6
8K @Q@+D85++66
=B@B"Q<B
+D8D68
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
36
?:!KN::O>BN%+DD?
04D
DH&9<IO+D4500/
+/P;KB>#"3
+D66 8=
++> Q<B +D8546/
+0%%B KP @
+D=8 +=4
+4B"<%+D8D=8+
+5 $K" N# B @" <
9<"+D=++?58
+6N#B@"<"+D=4
++==
+8B ";<" Q<@
+D=?5+=
+=;<"B"$ %&
B +D=D4=D
+?%@%K+D6445?
+D%B@Q@+D6=++6+
0/B@Q<@+D=D0=6
0+;KI<"*,+D58D6D
009KP*"B+DD6+588
049K*9B#Q<
B+DD=+0=
05#Q"*K3&Q<
B+DD?4=46
06 &@%&#P$I@
<@ "QK>0//+4445
08&PK#P$KO;K"C
@%&QK>0//406??
0=$I< !@%F!*
<%0//+D0+
0?>F"99OB"<
BBN0//4F+0
0D9OB"<@
0//5++4+
4/BBPK9B""
<BBN0//5<+6
4+BFPOB"<B
BN0//6Q+/
40HQNH9B<BB
N0//6F=
44B99%*OB"
<@0//6D=
45RN9OB"&<
99,"PB,<BB
N0//6F+=
469QK"BOB"B
0//6=00
48QK"PBOB"<%
0//648=D
4=QK"9OB"%
@0//60+//
4?R@KO#P$@%&Q
K>0//604/
4DN$QKKL"9N*O
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5/ BO B" Q<B
0//6@84D
5+PB>CKKPO<
%0//6+65
50KFC<% +DD=45?D
54KFCB@KKF
<%0//45+/=
55&CNQ!9NQ!HB9!H
NQPQ<B0//8F+8D
56KFC&*NP
B & B<%
0/// 0/0D
58$PKFCF@@
0//?
A. Popova, M. Christov
37
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 37-47
INHIBITIVE PROPERTIES OF QUATERNARY AMMONIUM BROMIDESOF N-CONTAINING HETEROCYCLES ON ACID MILD STEEL CORROSION
A. Popova 1, M. Christov 2
1 Department of Chemistry, Technical University of Sofia,
8 Kl. Ohridski, 1756 Sofia, Bulgaria2 University of Chemical Technology and Metallurgy,
8 Kl. Ohridski, 1756 Sofia, Bulgaria
ABSTRACT
!"# $ $
%&'(")
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$
")
+ ,
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01 $ $ $+ $&'$"
Received 23 November 2007
Accepted 12 December 2007
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
38
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EXPERIMENTAL
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Compounds Structural formulae Abbreviation Molar mass 1-(Carbamoylethyl)-4-methylpyridinium bromide
N+CH3
NH2
OBr-
CP
245.1
1-(Carbomoylethyl)-4- methylquinolinium bromide
N+CH3
NH2
O
Br-
CQ
295.2
3-(Carbomoylethyl)-2- methylbenzothiazolium bromide
S
N+
NH2O
CH3
Br-
CT
301.2
3-(3-Propylpyridinio)-2- methylbenzothiazolium bromide
S
N+CH3
N+
Br-
Br-
DBr
430.2
A. Popova, M. Christov
39
#
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RESULTS AND DISCUSSION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
40
$!
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Fig. 1. Inhibitor efficiency and adsorption isotherms of quaternaryammonium bromides in 1M HCl, experimental gravimetric data: – CP; - CQ; ∆ – CT; – DBr; calculated: ______ .
$?
? 1% 24K
polarisation curves EIS pol. res.
ci
(M)
Ecorr
(mV)
bc
(mVdec-1)
ba
(mV/dec)
jcorr
2)
Rct
2)
Cd
-2)
Ra
cm2)
Rpdc
(Ω cm2)
1M HCl -498±2 126±4.0 71±5.0 700±50 34.5±1.8 369±44 * 1-(Carbamoylethyl)-4-methylpyridinium bromide (CP)
10-5 -492±2 126±2 81±6 710±52 40.1±1.3 362±46 * 39.5±2.0 10-3 -498±2 141±3 120±2 570±12 70.2±2.2 223±24 * 71.9±2.0
2x10-2 -488±1 145±3 121±4 265±18 151±3 122±15 * 153±3 1-(Carbomoylethyl)-4- methylquinolinium bromide (CQ)
10-5 -500±2 127±3 78±4 718±63 42.5±1.8 381±40 * 41.9± 10-3 -490±1 138±6 121±4 542±31 84.5±3.1 307±35 * 86.1±2.7
2x10-2 -485±2 141±4 125±4 206±8 22.8±4.7 66±7 223±5 250±7 3-(Carbomoylethyl)-2- methylbenzothiazolium bromide (CT)
10-5 -500±2 128±3 89±2 689±51 61.7±7.1 257±27 * 67.0±4.3 10-3 -490±1 134±6 90±3 477±9 40.0±10.0 51±6 220±9 269±26
2x10-2 -479±1 144±2 114±4 104±5 52.4±4.1 41±4 359±3 419±12 3-(3-Propylpyridinio)-2- methylbenzothiazolium bromide (DBr)
10-5 -498±1 136±3 116±5 405±11 111±5 275±33 * 120±4 10-3 -483±3 139±65 116±5 110±10 15.5±0.5 47±5 221±11 243±11
2x10-2 -474±2 142±4 123±4 57±2 32.4±4.1 31±3 470±35 503±27
A. Popova, M. Christov
41
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Fig. 2. Arrhenius plot of mild steel corrosion in 1M HCl inpresence of 2x10-2 M of – CP; - CQ; ∆ – CT; –DBr; (R
p – method).
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
42
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Fig. 3. Inhibitor efficiency and adsorption isotherms of quaternaryammonium bromides in 1M H
2SO
4, experimental gravimetric data:
– CP; - CQ; ∆ – CT; – DBr; calculated: ______ .
A. Popova, M. Christov
43
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Compound θmax log B a 0adsG∆
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Standard
Deviation -log cθ=0.5
in 1M HCl CP 0.914 3.22 0.13 -27.8 0.014 3.28 CQ 0.933 3.71 -0.15 -30.6 0.020 3.64 CT 0.922 4.99 -1.06 -37.8 0.007 4.53 DBr 0.942 6.16 -2.02 -44.4 0.006 5.28 in 1M H2SO4 CP 0.975 2.81 0.86 -25.5 0.043 3.18 CQ 0.990 3.51 0.07 -29.5 0.022 3.54 CT 0.990 3.84 -0.09 -31.3 0.018 3.80 DBr 0.990 5.22 -0.92 -39.0 0.009 4.81
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
44
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Fig. 4. Structural model of the interface mild steel/1M HCl +inhibitors: a) at low concentrations (one-time constant model);b) at high concentrations (two-time-constants model)
A. Popova, M. Christov
45
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Fig. 5. Impedance diagrams for mild steel in 1M HCl + 1x10-2M DBr – complex plane plot (a) and Bode plot (b); experimental data;
............ calculated with Ra=409 Ω cm2, C
a=200 µF cm-2, n
a=0.75, R
ct=21.5 Ω cm2, C
d=29 µF cm-2, n
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
48
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 48-52
A VOLTAMMETRIC STUDY ON THE ELECTROCATALYTIC ACTIVITYOF A Pt OVERLAYER CHEMICALLY DEPOSITED ON Au SUBSTRATES
S. Kalcheva, P. Iotov
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail:[email protected]
ABSTRACT
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Received 23 November 2007
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INTRODUCTION
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S. Kalcheva, P. Iotov
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
50
Fig. 2. Arrhenius type plots expressed as ln ip (for the first anodic
peak) versus the reciprocal of temperature for Au substratesmodified by Pt. The surface content of Pt corresponds to 0.516(1), 0.316 (2) and 0.347 (3).
)
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Fig. 1. CV profiles for Au substrates modified by Pt taken at a sweep rate of 0.10 Vs-1. The profiles demonstrate the effect of temperatureincrease: 1 - 293.5 K; 2 - 298.1 K; 3 - 303.5 K; 4 – 308.5 K; 5 – 313.5 K. The surface content of Pt corresponds to 0.316 (a) and 0.433(b), correspondingly.
S. Kalcheva, P. Iotov
51
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Acknowledgements
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REFERENCES
C8:( D>(
-(E (F(*)$
,,9(::(++0($
$/7A(D4 (5CF(/7
A(46(E < 8(7G(**)(0$
Fig. 3. Apparent activation energy versus Au surface content for
Au substrates modified by Pt (-•-•-•) and for Pt + Au alloyelectrodes (---). The plot for the modified Au electrodes isbased on the temperature dependence of the first anodic peakcurrent density. The curve for the alloy electrodes is obtainedusing the data from ref. [18].
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
52
07,,(/7A(::A(++(
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M. Machkova, A. Zwetanova, V. Kozhukharov, S. Raicheva
53
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 53-58
THERMODYNAMIC TREATMENT OF CHROMIUMEVAPORATION FROM STEEL SOFC INTERCONNECTS
M. Machkova, A. Zwetanova, V. Kozhukharov, S. Raicheva
(This article is in memorium of prof. Svetla Raicheva)
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
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Received 23 November 2007
Accepted 12 December 2007
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
54
# 1 %
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M. Machkova, A. Zwetanova, V. Kozhukharov, S. Raicheva
55
9
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55. 5"( 5
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Fig. 1. Temperature dependence of partial pressures of Cr-oxidesover Cr
2O
3 (s) in dry air.
Fig. 2. Temperature dependence of partial pressures of Cr-oxyhydroxides over Cr
2O
3 (s) in humid air, rH 60%.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
56
G
=
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Fig. 3. Temperature dependence of partial pressures of mostabundant volatile Cr (VI) species over chromia, rH 60%.
Fig. 4. Temperature dependence of Cr-evaporation rate overchromia in dry air.
Fig. 5. Temperature dependence of partial pressures a) of CrO3
over Cr
2O
3 (s) and spinel in dry air, b) of CrO
2(OH)
2 over Cr
2O
3 (s) and spinel
in humid air, rH 60%.
a) b)
M. Machkova, A. Zwetanova, V. Kozhukharov, S. Raicheva
57
)$;-'
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Ebbinghaus [19] 2.4 x 10-4 0.1
Hilpert et al [2] 2.0 x 10-4 3.0 x 10-2
our results 3.5 x 10-3 1.6 x 10-4
; ;;1%=
Cr-evaporation rate / kg (Cr) m-2 s-1 Steel
calculated Experimental [22]
LH520 4.4 x 10-10 4.4 x 10-10
LH521 4.4 x 10-10 4.2 x 10-10
1
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
58
CONCLUSIONS
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E. Horozova, T. Dodevska, N. Dimcheva
59
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 59-64
MODIFIED WITH MICROQUANTITIES OF PLATINUM METALS GRAPHITES:APPLICATION TO THE DEVELOPMENT OF XANTHINE
OXIDASE ENZYME ELECTRODE
E. Horozova1, T. Dodevska2, N. Dimcheva1
1 Department of Physical Chemistry, Plovdiv University,
24, Tsar Assen st., 4000 – Plovdiv, Bulgaria2 Department of Inorganic and Physical Chemistry,
University of Food Technology,
26, Maritza blvd., 4002 – Plovdiv, Bulgaria
E -mails: [email protected]; [email protected]
ABSTRACT
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Received 23 November 2007
Accepted 12 December 2007
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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E. Horozova, T. Dodevska, N. Dimcheva
61
'JH8( 0F
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Fig. 1 SEM micrographs showing the surface morphology of modified graphites: A- 90%Pd:10%Pt/gmz (tdep
= 30 s); B- 90%Pd:10%Pt/gmz (t
dep = 90 s); C- 50%Pd:50%Pt/gmz (t
dep = 10 s); D- 70%Pd:30%Pt/gmz (t
dep = 10 s).
A) B)
C) D)
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
62
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E. Horozova, T. Dodevska, N. Dimcheva
63
Fig. 2 A - Steady-state response of the enzyme electrode as afunction of xanthine concentration at an applied potential -50mV (vs. Ag/AgCl); temperatures 25 0C and 30 0C; backgroundelectrolyte phosphate buffer, pH 8.4; Michaelis-Menten analysisin terms of Eadie-Hofstee (B) and Lineweaver-Burke (C) plotsbased on the data of figure 2-A (25 0C).
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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REFERENCES
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T. Vasileva, K. Stanulov, S. Nenkova
65
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 65-68
PHENOLIC ANTIOXIDANTS FOR FUELS
T. Vasileva, K. Stanulov, S. Nenkova
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
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Received 05 May 2007
Accepted 12 December 2007
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
66
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T. Vasileva, K. Stanulov, S. Nenkova
67
RESULTS AND DISCUSSION
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+-
44044$
Fig. 2. Gas-chromatogram of the mixture produced from lignin.
!
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$>7
-.
Fig. 3. Kinetic curves of the liquid paraffin samples oxidation at120oC.
Fig. 4. IR-specters of the oxidized liquid paraffin samples1. Unoxidized paraffin2. Oxidized at 120o C, with no additives3. Oxidized at 120o C, with 10 ppm ionol4. Oxidized at 120o C, with 10 ppm methoxyphenols5. Oxidized at 120o C, with 50 ppm methoxyphenols6. Oxidized at 120o C, with 500 ppm methoxyphenols
":
8,
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
68
$/$*0$
" F(($01*55%
*
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CONCLUSIONS
"
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REFERENCES
$:G<7H 7
$303,,$,,(
*:G<7:'F7H7
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A. Georgieva, D. Pishev, S. Veleva
69
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 69-72
INVESTIGATION ON APPLYING NATURAL SORBENTSFOR DECOLOURISATION OF DYE SOLUTIONS
A. Georgieva, D. Pishev, S. Veleva
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
!"#
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Received 05 May 2007
Accepted 12 December 2007
INTRODUCTION
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*+(,9-;:
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
70
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45<=&>?
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5
65
8 5 52 6 52 &6 52
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A&6<=( & 6
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=8
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: 557=
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RESULTS AND DISCUSSION
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A. Georgieva, D. Pishev, S. Veleva
71
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
72
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CONCLUSIONS(
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REFERENCES )JM= KN G42 4%
&)JM?= K. G44 22
2==O#.O-K= 1&555
!
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GG5 &6
6)JP(O1P-= K
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J9.:2&556 %6
O)0 / 2 GG6
G%
&.N?)JMMIMN=-
.& G446 %
2.;0-2 -=/
?= . G4%% 62
Fig. 1. Dependence of the quantity of adsorbed dye from theequilibrium concentration (Grus material, Priamoi krasnii 2C170 %).
Fig. 2. Dependence of the quantity of adsorbed dye from theequilibrium concentration (heat-treated Grus material, Acid BlackGLF conc.).
Fig. 3 Dependence of the quantity of adsorbed dye from theequilibrium concentration (bentonite “Zelenika”, Nylon FastYellow L-RPL)
Fig. 4. Dependence of the quantity of adsorbed dye from theequilibrium concentration (heat-treated bentonite “Zelenika”,Priamoi tshernii 2C 275 %).
S. Kozhukharov, G.. Tsaneva, V. Kozhukharov, J. Gerwann, M. Schem, T. Schmidt, M. Veith
73
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 73-80
CORROSION PROTECTION PROPERTIES OF COMPOSITE HYBRID COATINGS WITHINVOLVED NANOPARTICLES OF ZIRCONIA AND CERIA
S. Kozhukharov1, G. Tsaneva1, V. Kozhukharov1, J. Gerwann2,
M. Schem2, T. Schmidt2, M. Veith2
1University of Chemical Technology and Metallurgy
8, Kl. Okhridsky Blvd., Sofia – 1756, Bulgaria
E-mail: [email protected] fuer Neue Materialien,
Saarbruecken – Germany
Im Stadtwald, Gebäude 34A; 66123 Saarbrücken
ABSTRACT
!"#$ !%&#
'(&(&)
* +
%,%-.)&/'.
01 &)23
Received 20 September 2007
Accepted 12 December 2007
INTRODUCTION
! ""#$#%
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
74
%/0
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5
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S. Kozhukharov, G.. Tsaneva, V. Kozhukharov, J. Gerwann, M. Schem, T. Schmidt, M. Veith
75
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Index of the
sample
Name of the sample Constitution of the nanoparticle’s
containing layer
Curing time
at 120oC
(hours)
Total number of the layers
Thickness of the
nanoparticle’s
containing layer
Measured thickness of the
total coating
¯ X10
1 2 3 4 5 6 7
1 P1 AA2024 -- -- -- -- --
2 P2 Ref EADS -- -- 2 -- 34.5 ± 0.8
3 P3 Hydrophil + CeO2 Epoxysilane; Aminosilane with CeO2
8.6 wt% 4 1 5 - 7 7.3 ± 0.3
4 P4 Hydrophil + CeO2
EADS Epoxysilane; Aminosilane with CeO2
8.6 wt% 4 4 5 - 7 60.8 ± 0.6
5 P5 GMT 8%ZrO2 - 1h Ethoxysilane, metyltrietoxysilane with ZrO2
8 wt% 1 1 5 - 7 --
6 P6 GMT 8%ZrO2 - 1h EADS
Ethoxysilane, metyltrietoxysilane with ZrO2
8 wt% 1 4 5 - 7 --
7 P7 GMT 8%ZrO2 - 4h Ethoxysilane, metyltrietoxysilane with ZrO2
8 wt% 4 1 5 - 7 5.6 ± 0.3
8 P8 GMT 8%ZrO2 - 4h EADS
Ethoxysilane, metyltrietoxysilane with ZrO2
8 wt% 4 4 5 - 7 73.3 ± 0.7
9 P9 GMT 16%ZrO2 - 4h Ethoxysilane, metyltrietoxysilane with ZrO2
16 wt% 4 1 10 – 13 13.1 ± 0.7
10 P10 GMT 16%ZrO2 - 4h EADS
Ethoxysilane, metyltrietoxysilane with ZrO2
16 wt% 4 4 10 - 13 75.1 ± 1.4
11 P11 GMT 16%CeO2- 4h
Ethoxysilane, metyltrietoxysilane with CeO2
16 wt% 4 1 7 – 9 7.1 ± 0.6
12 P12 GMT 16%CeO2- 4h EADS
Ethoxysilane, metyltrietoxysilane with CeO2
16 wt% 4 4 7 - 9 74.9 ± 1.9
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
76
C
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RESULTS AND DISCUSSIONS
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6
Fig. 1. Dependence of OCP vs. the exposure time; (Index P-1) -the aluminum alloy; (P-2) – the polymer EADS coating; (P-7) -the sol-gel monolayer coating; (P-8) – multilayer coating,consisted on both of EADS and sol-gel layers.
Fig. 2. Polarization curves of (a)-sol-gel coating, (b)-EADSpolymer coating and (c)- combination of them; treatment 96hour exposure time in the corrosive medium; A- opticalmicrograph top view of a pitting effect .
S. Kozhukharov, G.. Tsaneva, V. Kozhukharov, J. Gerwann, M. Schem, T. Schmidt, M. Veith
77
$D#)
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6 7 7Rp 1.10 cm < Rp 1.10 cm < Rp 1.10 cm
hybrid referent combined
coatings coating coatings
≈ Ω ≈ Ω ≈ Ω
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
78
Fig. 3. Impedance spectra presented in Bode- (left) and Nyquist (right)- plots for referent coating P2, hybrid-composite coating P7 and thecombined coating P8.
< ! 5
3 !
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3
9
J
3
=2 JP/$/
( :#*,
8-
S. Kozhukharov, G.. Tsaneva, V. Kozhukharov, J. Gerwann, M. Schem, T. Schmidt, M. Veith
79
!
:%< &3
!=#=$ =#
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=$ P$$$.6
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Fig. 4. Impedance spectra dependence vs. the exposure time of the coatings: P2- referent sample, P10 (4 layers with ZrO2) and P12
(4 layers with CeO2); in Bode- (left) and Nyquist (right)- plots, respectively.
+/$!
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@0# '0
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
80
6
+7R %$
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REFERENCES81--1= S8-
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C.,
81
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 81-86
STUDY REGARDING THE NANO-HETEROGENEOUS STRUCTUREOF A TERNARY GLASS
C.1, 2
1 University,
Engineering Faculty,
3 Geneva Street, Targu-Jiu, Gorj, Romania
E-mail: [email protected] University of Bucharest, Faculty of
Applied Chemistry and Materials Science, Department
of Science and Engineering of Oxidic Materials and
Nanomaterials, 1-7 Polizu Street,
011061 Bucharest, Romania
ABSTRACT
!"
##
## #
$"#
% &
Received 05 May 2007
Accepted 12 August 2007
INTRODUCTION
! "
#$
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(
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4 4 3 1 2 2 1 3 4 2 4 2x x x x x xSiO Na Si O Na Si O Na Na O+ + + + ++ ↔ + ,-
" ,-'
(
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
82
21x
x
Si O
Si Si
N NK
N N+
⋅=
⋅ ,$-
(
1xSiN+
,&.
-/01 2
xSiN &
/01 2
/
2
2ON &
3 "
& &
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4
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50 99):7
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+:9)$7
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Fig. 1. Ternary diagram Na2O-CaO-SiO
2
C.,
83
MODEL DEVELOPMENTS
!
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x xf n∑
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x x
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/0$
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x xnx
x x
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& '
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n=
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RESULTS AND DISCUSSION
$0
Fig. 2. Polymers distribution in the melt in the Na2O – SiO
2
system.
Fig. 3. Polymers distribution in the melt in the CaO – SiO2
system.
Fig. 4. The variation of basicity gravity of the structural aggregatespecies. On the abscissa there was represented the number of xsilica atoms of every species
Basicity weight factor
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
84
)/0$ 50)/0
$ *$
+
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50)
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3
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3st NaSi NaSi CaSi CaSipB pB c pB c= + ⋅ ,-
Fig. 5. The variation of basicity gravity of the structural aggregatespecies. On the abscissa there was represented the number of xsilica atoms of every species
Fig. 6. Basicity gravity variation of the structural aggregate species.On the abscissa there was represented the number of x silicaatoms of every species.
Fig. 7. The values of the dilatation coefficient of aggregatedspecies according to the distribution.
C.,
85
' >+
? 9:61:
9:88
&
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917 $0)/0
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CONCLUSIONS
, -
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$ 50)/0
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REFERENCES
%B;C 5/
$::6 $+$+$6
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
86
M/ D 0&;
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N. Verma, D. Mewes, A. Luke
87
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 87-92
NON-UNIFORMITY IN VELOCITY AND CONCENTRATION PROFILESIN A NARROW TUBULAR ADSORBER
N. Verma1, D. Mewes2, A. Luke2
1Department of Chemical Engineering
Indian Institute of Technology Kanpur
Kanpur - 208016, India
E-mail: [email protected] of Thermodynamics
Leibniz University of Hannover
Hannover - 30167, Germany
ABSTRACT
! "#
$ %
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$
$
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*+ "#
Received 05 October 2007
Accepted 12 January 2008
INTRODUCTION
!
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
88
-*.-/+
0
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#
$2
.-/ 34
#
5!
5
5
MACROSCOPIC GOVERNING EQUATIONS
" #
#
6
)/(g
dCs
dCg
Cts
Ct
∂=∂ *+
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tam
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MESOSCOPIC LBM EQUATIONS
.-/#
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9 &3'
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fi
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7
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N. Verma, D. Mewes, A. Luke
89
9
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TEST CALCULATION
.-/
2*
+
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"+G H*1+
2
) (
Fig. 1. Packed bed adsorber: breakthrough curves, concentration profiles and contours.
Fig. 2. Lattice Boltzmann modeling of flow past a square and a circular cylinder confined in a rectangular channel.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
90
"
$
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&B'
I*(+ *456
+
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RESULTS AND DISCUSSION
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Fig. 3. Velocity vectors for x-z planes located at y = 0 and y = rp
in 3-spheres triangular packing with 1-sphere placed alternatelyalong x-axis
Fig. 4. Concentration profiles across cross section of tubular bed att=1000 s: effect of diffusivity on the concentration profile.
N. Verma, D. Mewes, A. Luke
91
Fig. 5. Schematic of the experimental set-up used for concentration measurements in a tubular adsorber using tomography technique.
* +
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
92
34
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CONCLUSIONS
34)
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Acknowledgements
9 : 1&
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REFERENCES
K; /K M 4/
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H O9Q *3(+ ??( 3B?
EI9/ I9- 4K: G-
-/H Q
) B ??A BDD
A$) 4F G-
-:;H O/
Q D ??D (B
B/- O- R )4 G"
#
6
- H OF)
) ( DA
D;9 M 4/ G
H
1M9 (E E(
?9 ; *(E+
Q4 Q T
F :
Fig. 6. Experimental data and model results for breakthroughcurves at the center and near the periphery of the adsorber packedwith glass coated zeolites.
M. Minceva, J. Taparcevska, L. Markovska, B. Koumanova, V. Meshko
93
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 93-100
ADSORPTION KINETICS OF Pb2+ ONTO NATURAL ZEOLITE
M. Minceva1, J. Taparcevska2, L. Markovska2, B. Koumanova3, V. Meshko2
1 University Erlangen, Egerlandstr.
3D-91058 Erlangen, Germany2 Faculty of Technology and Metallurgy,
SS. Cyril and Methodius University,
P.O. Box 580, MKD-1001 Skopje,
Republic of Macedonia
E-mail: [email protected] University of Chemical Technology and Metallurgy,
8 Kl. Ohridski, 1756 Sofia, Bulgaria
ABSTRACT
!"#$%
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( $
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)(*&
Received 05 December 2007
Accepted 12 February 2008
INTRODUCTION
!"
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)
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
94
+!(
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9
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M. Minceva, J. Taparcevska, L. Markovska, B. Koumanova, V. Meshko
95
EXPERIMENTAL
Materials and methods
( >&7
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RESULTS AND DISCUSSION
SORPTION ISOTHERMS
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
96
( #
>&7-
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#
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G'
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(&> # >&7-
Fig. 1. Comparison of experimental and calculated data byLangmuir and Freundlich equilibrium isotherms for the systemPb2+ - natural zeolite. - Experimental data ____ - Langmuirisotherm -------- - Freundlich isotherm
0
10
20
30
40
50
0 20 40 60 80
cmg dm3
q , m
g g
Fig. 2. Effect of agitation speed for the system Pb2+ - naturalzeolite (c
o=250 mg dm-3, d
p = 1100 mm, m=1 g, T=25oC). - 150
rpm, 175 rpm, - 190 rpm.
Langmuir isotherm
Freundlich isotherm
b dm3 g-1
Q0 mg g-1
R2 KF
mg g-1 n R2
1.004 32.97 0.997 16.059 4.56 0.946
M. Minceva, J. Taparcevska, L. Markovska, B. Koumanova, V. Meshko
97
( 12
-
%
( -
- /22 *22
12&+2
' &+
( -
%$'9>&7
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#
5
:#.
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I&+2'I (I&+
I/22
µ;I122µ;
I 22µ; J
I *22µ
Fig. 4. Effect of initial concentration for the system Pb2+ - naturalzeolite (190 rpm, d
p =1100 mm, m=1 g, T=25oC). c
o = 50 mg
dm-3 co = 100 mg dm-3 c
o = 150 mg dm-3 c
o = 250 mg dm-3 *
co = 500 mg dm-3
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
98
)(1 tet qqk
dt
dq−= .
),
I2212
2
:#.
:#/,
tk
qqq ete 303.1)log()log( 1−=− /
) &%
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-
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(
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5 &+!
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:#0
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t qqkdt
dq−= 0
):#0 ,
I2I2 I
2
:#1,
tqqkq
t
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112
2
+= 1
) &
3
-(
1
! !!'% !'%% !!"% !'''%
!! !! !' !! '' !'''
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!! !!! !'%'' !!! % !'''
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M. Minceva, J. Taparcevska, L. Markovska, B. Koumanova, V. Meshko
99
Fig. 5a. Pseudo-first order reaction kinetics plots for the systemPb2+ - natural zeolite (first period), (190 rpm, d
p =1100 mm, m=1
g, T=25oC). co = 50 mg dm-3 c
o = 100 mg dm-3 c
o = 150 mg
dm-3 co = 250 mg dm-3 * c
o = 500 mg dm-3.
Fig. 5. Pseudo-first order reaction kinetics plots for the systemPb2+ - natural zeolite (190 rpm, d
p =1100 mm, m=1 g, T=25oC).
co = 50 mg dm-3 c
o = 100 mg dm-3 c
o = 150 mg dm-3
co = 250 mg dm-3 * c
o = 500 mg dm-3.
Fig. 5b. Pseudo-first order reaction kinetics plots for the systemPb2+ - natural zeolite (second period), (190 rpm, d
p =1100 mm,
m=1 g, T=25oC). co = 50 mg dm-3 c
o = 100 mg dm-3 c
o = 150
mg dm-3 co = 250 mg dm-3 * c
o = 500 mg dm-3.
%
3
$.D3
-
( &
#
-
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)('
%(
3
L211.
CONCLUSIONS
%-,
( #
D#
$
$ %
Fig. 6. Pseudo-second order reaction kinetics plots for the systemPb2+ - natural zeolite, (190 rpm, d
p =1100 mm, m=1 g, T=25oC).
co = 50 mg dm-3 c
o = 100 mg dm-3 c
o = 150 mg dm-3 c
o =
250 mg dm-3 * co = 500 mg dm-3.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
100
$
%
M
$ %
-
=
)
%
Acknowledgements&(
4/56
44/5
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REFERENCES
M$%K&222.2:9
&222
& N=% )9%"> N9-%
NK 8O 5(N=-"
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'($O: >
:>>=
>(P<9P 111
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+K?9KM(
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.A" %DB"%%""%% ) N
:> *&22.&0+&11
/""D"%%A" %"N
:&&22/ &+ '*
0?O-O5%%$@-MP
&22' 1*01+&
1"" 55%99N=-" 1
' &22+ 0' 00
2 9858 5K-OO
O5 &222 // 0*
54>N)==PN
95,> :
5 ++ 111.'.0
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&' 0
'(58@O9 M=D94
9(:&'&22.*21*&.
*?5=??-(KN)9
110 '2 *2
+55N5@--@DQD9
6("" 11. G '
.64989>( &22*
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/"94"-PDP>5
KD$PP"@
N)9'2 &22.*2*+
0"-"OR-9>( &22*
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1<M 46%@ $P
9 MP&22+'&0/G'&1/
&28= N=-"&22&//G1+
& D"%%A" %""%%N9
9 0G1&22.1+/G1./
&&"(N>6A%B"N=-
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9 10&*&+ *&.
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PK@>>
4&22
A. Maximova, B. Koumanova
101
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 101-108
EQUILIBRIUM AND KINETICS STUDY OF ADSORPTIONOF BASIC DYES ONTO PERFIL FROM AQUEOUS SOLUTIONS
A. Maximova, B. Koumanova
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
!"#
# #$ !"$ ##
% & #' #!" (#
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)!"*#%
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+, $ ##*!
Received 05 May 2007
Accepted 12 December 2007
INTRODUCTION
!"#
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
102
#
-!%!&
!'!(7!)!*
#
4
#4 "
- ##
1$+
891)9
9&:
4
EXPERIMENTAL
#9/4
91)99&
#
0
"# #
#
91)
Fig.1. Structure of the basic dyes.
99&
94
.#
"
#
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#4#25
++25&+;9<"=
6
2;2<
#2
4.!%>
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8!++!&+?:
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@4ABC,"
#
8D :%)*91)'+9
9&##
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G#
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5&+:##&+
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#
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!+I!
A. Maximova, B. Koumanova
103
#
8:
w
VCCq eo
e
).( −= 8:
#
8$:J+J G
8$:#
8:
"4#
4 8($:
!+I!##
#
"
#
8-+!H:
#-
RESULTS AND DISCUSSION
"
#
@
5
3
& #
.
1 .L e
eL e
K Cq
a C=
+ 1
.e Le
e L L
C aC
q K K= + 8!:
'
. Fne F e
q K C= log log .loge F F eq K n C= + 8$:
!
"#$
$#
!
"#%&$
&#
Fig. 2. Adsorption isotherms and linearized models of Basic red 18 on Perfil M-100 and Perfil M-150. (a) onto Perfil M-100; (b) linear Freundlich model; (c) on Perfil M-150; (d) linear Langmuir model.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
104
.
1 .R e
e bR e
K Cq
a C=
+ 8%:
#
K
5
4E
- "
4
0!! # 9
1)25++25&+
#-$
C
2
91)EJ$&
#3E
0!#-.$
-
/L
00!
99&
0
91)
#
#
99&9
1)##25
++M25&+099
&+M25++
#/12
"
0
225++25&+
"#&&
$&&#
$
&
&
Fig. 3. Linear Redlich-Peterson model for the system Basic Blue 5on Perfil M-100.
"#$$
$&#
Fig. 4. Linear Langmuir model for the system Basic Blue 5 onPerfil M-150.
Dye-sorbent system
Langmuir model kL aL R2
Freundlich model kF nF R
2 Redlich-Peterson model
kR aR b R2 qemax
Basic Red 18 with
Perfil M-100 (Co = 3-24 mg dm-3) Perfil M-150 (Co = 3-15 mg dm-3)
0.6191 0.1473 0.8020 2.6889 0.2422 0.8674
0.5389 0.6945 0.9244 1.6315 0.4987 0.7215
0.6191 0.5418 0.6764 0.8154 3.02 2.6889 0.7229 0.8200 0.7086 2.81
Basic Blue 5 with
Perfil M-100 (Co = 3-10 mg dm-3) Perfil M-150 (Co = 3-24 mg dm-3)
0.4416 0.1060 0.2717 2.5491 0.5390 0.9673
0.4604 0.7144 0.7592 0.8243 0.6358 0.9192
0.4416 0.0544 1.3776 0.9577 1.36 2.5491 0.8985 1.0646 0.9363 1.87
A. Maximova, B. Koumanova
105
91)25++
0 9 9 & 25++
1299
&25&+/1
2#
Adsorption kinetics
"4
#
@
4#4
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$!4 $$
#8&:8':
tk
qqq ete .303.2
log)log( 1−=− 8&:
22
1 1.
t e e
tt
q k q q= + 8':
#4
4!
C 8&:
#
1-.(1- )k tt eq q e= 8(:
3
22.( )eh k q= 8):
#4!
4
!24
Dye system Pseudo-first order model K1 qe R
2
min.-1 mg g-1
Pseudo-second order model K2 qe2 R
2
g mg-1min-1 mg g-1
Initial speed of the adsorption, h mg g-1 min-1
Basic Red 18 on Perfil M-100 w=1 g n=200 rpm Co= 5 mg dm-3 Co=10 mg dm-3 Co=15 mgdm-3 Co=10 mg dm-3 n= 200 rpm w=1 g w=2 g w=3 g Co=10mgdm-3 w=1g n= 100 rpm n= 200 rpm n= 300 rpm Basic Blue 5 on Perfil M-100 w=1g n=200 rpm Co= 5mg dm-3 Co=10mg dm-3 Co=15mg dm-3 Co=10mg dm-3 n=200 rpm w=1 g w=2 g w=3 g Co=10 mg dm-3 w=1 g n=100 rpm n=200 rpm n=300 rpm
0.0403 0.1101 0.7359 0.0389 0.4522 0.7493 0.2593 0.1059 0.9002 0.0389 0.4532 0.7491 0.1663 0.6084 0.8345 0.0940 0.5378 0.9342 0.7190 0.3338 0.9538 0.0421 0.9304 0.8869 0.0359 0.4586 0.8768 0.2225 2.44 0.9133 0.1485 4.69 0.9798 1.3555 23.12 0.9447 0.2190 4.1476 0.9422 0.2420 0.4801 0.9604 0.2913 0.9333 0.9453 0.7190 0.3338 0.9522 0.0421 0.9304 0.9798 0.0359 0.4586 0.9891
2.8475 6.71 1.0000 0.5291 12.82 1.0000 9.5425 18.69 1.0000 0.5028 12.82 1.0000 0.5781 6.61 0.9998 0.7215 4.83 0.9999 0.9328 11.88 1.0000 0.5028 12.82 1.0000 0.5741 13.00 1.0000 0.1369 10.14 0.9989 0.0998 14.08 0.9998 0.7060 18.59 1.0000 0.0998 14.08 0.9998 0.3845 7.35 0.9999 0.9948 5.28 1.0000 0.1246 13.19 0.9998 0.0998 14.08 0.9998 0.0990 14.22 0.9997
128.21 86.96 333.35 82.65 25.25 16.81 131.58 82.65 97.09 14.08 19.78 243.99 19.80 20.79 27.70 21.69 19.80 20.04
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
106
0&(9
1)99&
44
.
#
#
#
625++
25&+#
8
:0((
"#$%&
#
"#&%
#
"#%
#
'#
'#
'#
Fig. 5. Pseudo-second order kinetics of Basic Red 18 on Perfil M-100 (w = 1 g, n = 200 rpm).
"#%&
#
"#&$%
#
"#&%
#
&
#(
#(
#(
Fig. 6. Pseudo-second order kinetics of Basic Red 18 on Perfil M-100 (C
o = 10 mg dm-3, w = 1 g).
Fig. 7. Kinetics models of Basic Blue 5 and Basic Red 18 on Perfil M-100. (a) Pseudo-first order kinetics of Basic Blue 5 (Co = 10 mg dm-3);(b) Pseudo-second order kinetics of Basic Blue 5 (Co = 10 mg dm-3, n = 200 rpm); (c) Pseudo-second order kinetics of Basic Blue 5 (Co =10 mg dm-3, w = 1 g); (d) Pseudo-first order kinetics of Basic Blue 5 (Co = 10 mg dm-3, w = 1 g).
"#&%
#$$$
"#&%$$
#$$$&
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#(
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A. Maximova, B. Koumanova
107
#
4/
N #
+**)+#
.
#
8 !:
'(
!)!91)+%%+)
99&
CONCLUSIONS
25++25
&+#9
1)99& #
#
#
44
4
25++25&+#
##
4#
Aknowledgements
"* *
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REFERENCES
G50EE1"OP
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!B.4,"P#
,4=46
*)81:
$L56 @ B" . 25 BE1
P.C2=!
=*)%!!
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& @B"96 BF
58@:$!++&(&*!
'5P4/1PP1!**(
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(L56E@9B1LB"2
@!*)!$+%$
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1!*)+&
*GB2L56BBEP1!
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+@CL"@! **$+*
QEE@AQ0E5"P
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9!**!&(!)%
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!+@B2L=0#B@12
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!=12""
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*)(+%+
!'1=04=B6#61E .C
0!*($*&
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!*7@!**%'(
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
108
$+@51P="E9".C
B!**%!+%&
$P".552C%C,#
74
$!7@E"B."
@!++$*%(
$$7@EL5629***
%&%'&
P.K. Igbokwe, R.O. Okolomike, S.O. Nwokolo
109
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 109-112
ZEOLITE FOR DRYING OF ETHANOL-WATER AND METHANOL-WATER SYSTEMSFROM A NIGERIAN CLAY RESOURCE
P.K. Igbokwe, R.O. Okolomike, S.O. Nwokolo
Department of Chemical Engineering
Nnamdi Azikiwe University, P.M.B. 5025,
Awka Anambra State, Nigeria
E-mail: [email protected]
ABSTRACT
!!"#$%&'!!())!"#
((%
%*
%+
%
,-%
Received 05 October 2007
Accepted 12 February 2008
INTRODUCTION
!
" #
$
%&'(
%)(
*
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
110
*
# $
+
+" ,
,
+ &'
%-(
.
EXPERIMENTAL
*
+
/
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0 #"* $
1 23345
&6
7
0
83345
/
9
RESULTS AND DISCUSSION
:& 0
0
" %6(
; "
:'8
# 7< $
Fig. 1. IR spectra of the zeolite produced.
P.K. Igbokwe, R.O. Okolomike, S.O. Nwokolo
111
# -< $
%-(
+
%2(5
CONCLUSIONS
+
+
,
REFERENCES
&*=>:?=; @1
* A / !B
" C"1A)2
- &D7D &733&D2&
'?/"5,EC,A
5/8&D76')'7
)0*9; *AFA
5 +B,G&D27
-0/H>**?1+A
1 -'2&&)3&D7&
Fig. 2. Breakthrough curve for water in ethanol using syntheticzeolite.
Fig. 3. Breakthrough curve for water in methanol using syntheticzeolite.
Fig. 4. Breakthrough curve for water in ethanol using kaolin.
Fig. 5. Breakthrough curve for water in methanol using kaolin.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
112
85,E1>+ 5
* A&D76
6>B9; *AA 5
+B ,G&D2-
2*"1*
86'33'7&77
K. Shanmugam, K. Saravanan, V. Ramamoorthy, R.Balasubramani
113
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 113-118
HYDRODYNAMIC STUDIES IN STIRRED BUBBLE COLUMN
K. Shanmugam1, K. Saravanan1, V. Ramamoorthy2, R.Balasubramani1
1Department of Chemical Engineering,
Kongu Engineering College, Perundurai,
Erode-638052, India
E-mail: [email protected] of Chemical Engineering,
Anna University, Chennai-600 025, India
ABSTRACT
!
" ""#$%&
#'()& #*& + ,
-./)01
234
+5
! "
*' 60 7
0 *
8 9
Received 05 October 2007
Accepted 25 February 2008
INTRODUCTION
!
"
!
!
#
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
114
!$
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% ! )
6*#
7)8$/
!
$
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;#
<
< *7*77
! "
!=
!
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> $
%
%
/:
Fig. 1. Stirred Bubble Column Set up.
K. Shanmugam, K. Saravanan, V. Ramamoorthy, R.Balasubramani
115
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EXPERIMENTAL PROCEDURE
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RESULTS AND DISCUSSION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
116
2@A ,:0
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Fig. 2. Effect of superficial gas velocity on fractional gas hold upfor H/D ratio of 4.
Fig. 3. Effect of superficial gas velocity on fractional gas hold upfor 1.5 % NaCl solution.
Fig. 4. Effect of stirrer speed on fractional gas hold up.
1.5% NaCl Solution
0
0.2
0.4
0.6
0.8
1
1.2
0.054 0.081 0.108 0.135 0.162 0.19 0.217 0.244 0.271
Superficial Gas Velocity (m/s)
Frac
tiona
l Gas
Hol
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50 RPM
100 RPM
150 RPM
200 RPM
250 RPM
2% NaCl Solution
0
0.2
0.4
0.6
0.8
1
1.2
50 75 100 150 200 250
Speed of the Stirrer (RPM)
Frac
tiona
l Gas
Hol
dup
50 lpm
100 lpm
150 lpm
200 lpm
250 lpm
K. Shanmugam, K. Saravanan, V. Ramamoorthy, R.Balasubramani
117
%
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Fig. 5. Effect of concentration of NaOH solution on fractionalgas hold up.
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Fig.7. Effect of H/D ratio on fractional gas hold up.
NaOH Solution, 150 RPM
0
0.5
1
1.5
2
2.5
0.0541 0.1083 0.1624 0.2165 0.2706
Superficial Gas Velocity
Frac
tiona
l Gas
Hol
dup 1%
1.50%
2%
At 150 RPM, 2% Solution
0
0.5
1
1.5
2
2.5
0.0541 0.1083 0.1624 0.2165 0.2706
Superficial Gas Velocity (m/s)
Frac
tiona
l Gas
Hol
dup
water
NaCl
BaCl2
NaOH
MgCl2
At 150 RPM
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0.054 0.081 0.108 0.135 0.162 0.19 0.217 0.244 0.271
Superficial Gas Velocity (m/s)
Frac
tiona
l Gas
Hol
dup
H/D = 2
H/D = 3
H/D = 4
H/D = 5
H/D = 6
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
118
% !
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REFERENCES
)<H $## D%
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Fig. 8. Effect of stirrer on % gas hold up for tap water/air system.
% Holdup at 150 LPM
0
10
20
30
40
50
60
70
1 2 3 4 5 6
H/D ratio
% G
as H
oldu
p column with stirrer
column without stirrer
S. Diankov, E. Simeonov, K. Tomova
119
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 119-124
MODELLING OF MULTISTAGE EXTRACTION KINETICSFOR NICOTIANA TABACUM L. – WATER SYSTEM
S. Diankov, E. Simeonov, K.Tomova
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
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Received 05 December 2007
Accepted 12 February 2008
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
120
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RESULTS AND DISCUSSION
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S. Diankov, E. Simeonov, K. Tomova
121
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Fig. 1a. Influence of the initial concentration on the first stageyield.
Fig. 1b. Influence of the initial concentration on the secondstage yield.
Fig.2a. Influence of the effective diffusivity on the first stageyield.
Fig. 2b. Influence of the effective diffusivity on the second stageyield.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
122
&
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Fig. 3a. Influence of the porosity on the first stage yield.
Fig. 3b. Influence of the porosity on the second stage yield.
)
63
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Fig. 4. Variation of the concentration at the particle surface intime.
Fig.5a. Experimental and numerical data comparison, ζ=0,01.
Fig. 5b. Experimental and numerical data comparison, ζ=0,02.
Fig. 5c. Experimental and numerical data comparison, ζ=0,03.
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S. Diankov, E. Simeonov, K. Tomova
123
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REFERENCES
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
124
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Mohammad Reza Poor Heravi
125
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 125-128
STUDY OF MASS SPECTRAL MCLAFFERTY FRAGMENTATIONOF βββββ-KETOSULFIDES AND βββββ-KETOSULFONES
Mohammad Reza Poor Heravi
Department of Chemistry,
Abhar Payame Noor University, p.o. box 97,
Abhar, Iran.
E-mail: [email protected]
ABSTRACT
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Received 05 September 2007
Accepted 25 February 2008
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
126
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m/e=65(32%)
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m/e=105(100%)
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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REFERNCES
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M. M. El Jamal
129
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 129-138
EXPERIMENTAL E-pH DIAGRAMS OF Fe(III)/Fe(II) SYSTEM IN PRESENCEOF VARIABLE CONCENTRATION OF DIFFERENT LIGANDS
M. M. El Jamal
Faculty of Science, Chemistry Department,
Lebanese University, El Hadath, Lebanon
E-mail: [email protected].
ABSTRACT
!
!! !"! " #
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Received 05 May 2007
Accepted 20 December 2007
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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M. M. El Jamal
131
. 0?
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
132
RESULTS AND DISCUSION
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YHIIFeeHYFeIII4)(14][ +→++
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)( likelymost
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2
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7B>(
% (-.
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][ 4−Y :
)]([
)]([log06.077.0'
2
−
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III
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ββ
'
F3'+2 : =+− 21080 "#B>'
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3
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%:
OHYFeeHHYOHFe II2
233 3]12)( [ +→+++ −
←−+−
or
OHYFeeHYOHFe II2
243 3][13)( +→+++ −
←−+−
'(
% F
-.%%
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M. M. El Jamal
133
3%
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2 4 2 2 4[ ( ) ] 2 1 ( ) 2IIIFe C O H e Fe II HC O− + − −←+ + → +
( %% :
32 4 3[ ( ) ] 2 1IIIFe C O H e− + −
←+ + →
22 4 2 2 2 4[ ( ) ]IIFe C O H C O−
←→ +
B'"??B'B/
%(%( (JA
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( %:
3 22 4 3 2 4 2[ ( ) ] 1 [ ( ) ]III IIFe C O e Fe C O− − −
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2 22 4 2 4( 0.06 )C O E cte pC O− −+ = −
D
!?0
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3 42 4 3 2 4 3[ ( ) ] /[ ( ) ]III IIFe C O Fe C O− − '
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53%
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'3(
23 3 =
-400
-300
-200
-100
0
100
200
300
400
500
600
0 1 2 3 4 5 6 7 8 9 10
pH
E (
mV
)
2.5 ml EDTAExp.Fe(III)/Fe(II) alone5 ml EDTA10 ml EDTA7.5 ml EDTATh. curve + 0.1 M EDTA Th. Fe(III)/Fe (II) alone
A
BC
D
Fig. 1. E-pH diagrams of Fe(III)/Fe(II) in presence of variablevolume of 0.1 M EDTA.
-200
-100
0
100
200
300
400
500
600
700
800
900
0 1 2 3 4 5 6 7 8 9 10 11 12
Volume of KMnO4
E (
mV
)
Fe (II) alone
5 ml EDTA
10 ml EDTA
3 ml EDTA
1 ml EDTA
Fig. 2. Titration curves of 10 ml of 0.1 M of Fe(II) with KMnO4
in presence of variable volume of 0.1 M of EDTA.
-400
-300
-200
-100
0
100
200
300
400
500
600
0 1 2 3 4 5 6 7 8 9
pH
E (
mV
)
20 mL oxal15 mL oxal10 ml oxalFe(III)/Fe(II) alone5 ml oxal
A
B
C
in absence of oxalate
Fig. 3. E-pH diagrams of Fe(III)/Fe(II) in presence of variablevolume of 0.125 M oxalate.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
134
(3 3 (
'%
-.'
3%(3
%3'F #'4
2 7B>3'. . '
!! !!
3% (
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% %
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3 ( %
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2 B'"??B'B/ '< %(
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3 2[ ( ) ] 2 1IIIFe CH COO H e+ + −←+ + →
3( ) 2Fe II CH COOH←→ +
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salicylic acid+
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-400
-300
-200
-100
0
100
200
300
400
500
600
0 1 2 3 4 5 6 7 8
pH
E (
mV
)
Fe (III)/Fe (II) alone
0.025 M acetic acid
0.075 M acetic acid
1 M acetic acid
0.5 M acetic acid
A
B
Fig. 4. E-pH diagrams of Fe(III)/Fe(II) in presence of variablevolume of 0.1 M acetic acid.
M. M. El Jamal
135
%3( :
3%(?
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0 E B !4 3
( %:
3( ) 3 1 ( )IIIFe citrate H e Fe II H citrate+ −←+ + → +
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2 B'B/
(C3 :
32[ ( ) ] 1IIIFe citrate H e− + −
←+ + →2[ ( )]IIFe citrate Hcitrate− − −
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2 % %3
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(%
% #'
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("B?*>3%
0
100
200
300
400
500
600
700
800
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10
volume of K2Cr2O7
E(m
V)
0.3g citrate
0.145g citrate
Fe (II) at pH 3
Fe (II) at pH 1
0.23g citrate
Fig. 5. Titration curves of 10 ml of 0.1 M Fe(II) at pH 3.2 inpresence of variable mass of tri sodium citrate.
!"
# $%
Fig. 6. E-pH diagrams of Fe(III)/Fe(II) in presence of o-phen.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
136
% %Q'* !;$'
3 %33
3
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%
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-500
-400
-300
-200
-100
0
100
200
300
400
500
600
0 1 2 3 4 5 6 7 8 9 10
pH
E(m
V)
Fe(III)/Fe(II) alone
0.22g KCN
0.115 g KCN
0.03g KCN
0.05g KCN
Fig. 7. E- pH diagrams of Fe(III)/Fe(II) in presence of variablemass of KCN.
M. M. El Jamal
137
.DN<'42 B'"#B'B/?
(:
2[ ] 2 1 ( ) 2IIIFe F H e Fe II HF+ + −←+ + → +
( 0.12 )E cte pH= − ×
%(<'44'4
(( %
(C3 :
2[ ] 1 ( ) 2IIIFe F e Fe II F+ − −←+ → +
3 1 ( ) 3IIIor Fe F e Fe II F− − −←+ → +
CONCLUSIONS
3%
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%%
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Acknowledgements
%
#
REFERENCES
"'T' *'* P'P
2*U
@ ";5?'
?'*'PQ'-D'.'Q-'D
& 2
2&3@";;B'
#'Q'* Q'&'V D
'P";;/'
<''D'. 'P -'@3
2?'-@?BB#'
4'D' 2
"*@";;#'
/' @'* Q'' * + 2
>%@";5;'
5'Q'K'T D'D 2
2 F2
&3@";7;'
7'&'* 'Q'D '';""";#"'
;'Q'* Q'P"BB*
D 'P
D?BB"'
"B'-''V3 .
'8'',(K)";;4'
""'*'*'Q 'Q'93'' '
*'+<?"?BB5'
-400
-350
-300
-250
-200
-150
-100
-50
0
50
100
150
200
250
300
350
400
450
500
550
0 1 2 3 4 5 6 7 8 9
pH
E (
mV
)
Fe(III)/Fe(II)alone
0.42g NaF
0.3g of NaF
0.2g of NaF
0.14g NaF
0.1g of NaF
0.07g of NaF
A
B
B'
Fig. 8. E- pH diagrams of Fe(III)/Fe(II) in presence of variablemass of NaF.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
138
"?'P'P-'DQ'-% 2
2*@";;"'
"#'T Q'D'&% D'
2 & 2
F *U@";4;'
"<'T' *'* P'P 2
>*@";5/'
"4'T' & 2
&F 2 3/'*U
@";/;'
M. Georgiev, V. Karadjova, D. Marinova, D. Stoilova
139
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 139-148
STUDY ON THE HYDRATES OF BERYLLIUM SULFATE AND SELENATE: THERMALANALYSIS, X-RAY DIFFRACTION AND INFRARED SPECTROSCOPY
M. Georgiev1, V. Karadjova1, D. Marinova2, D. Stoilova2
1 University of Chemical Technology and Metalurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail:[email protected] Institute of General and Inorganic Chemistry
Bulgarian Academy of Sciences,
“Akad. G. Bonchev” str., bl.11, 1113, Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
!
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Received 05 October 2007
Accepted 23 January 2008
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
140
!" -(
-(
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&*+)6
&7)
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EXPERIMENTAL
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RESULTS AND DISCUSSION
9&.)-($(
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M. Georgiev, V. Karadjova, D. Marinova, D. Stoilova
141
%9%88%-0 -($(
-($(
6 <9
%88
-($(
*2 /0
+2/0
+2 K **2 /0 6
''*'(1 * 7*/0
%8
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/0
* 7*/0K
B
8
-($(
%98
-($(
%-0!
''2 ''72< '.< <*2 /0 6 <"
%-0
-($
'<*'77/0 %8
A
Fig. 1. Projections of the crystal structures of BeSeO4.4H
2O and BeSO
4.4H
2O along the a
1-axis.
Fig. 2. DTA, DTG and TG curves of: a, BeSeO4.4H
2O; b,
BeSO4.4H
2O.
-((
→ -
(<
→ -
(
→
-(
→-
(
-((
&'')
%9%8%-0
A
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
142
-((
→ -
(
→ -
(
→
-(2*
→ -
(
%-0∆
-($(
→ -
(#(
<(2L'∆
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-(
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*/0,
!J*+* !'"ÅMJ.72*! "ÅM
J(* 2!'"ÅM9J (.+!7"Å<"
,'-(
,
!J*1(<! "ÅMJ.+.2!<"ÅMJ
(7. !'"ÅM9J 71(Å<"-(K
! J (7(1!'"ÅM J +21(!<" ÅM9 J
'*<'!'" Å<" &'')G
B
-(
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*/0
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, ":-($(
, +'.(3 -
(
!''3
27(3
+ +(3 &*)"
K
&! "
() #-
(
#
-(
'!Å" -($
Fig. 3. DSC curves of: a, BeSeO4.4H
2O; b, BeSO
4.4H
2O.
M. Georgiev, V. Karadjova, D. Marinova, D. Stoilova
143
&!
(") #
-(
-($(
!4("
Aν
'!9
'"
4ν !H"
--(
-
(
*/0
Fig. 4. Solubility diagram of the BeSeO4 - H
2SeO
4 - H
2O system at 25 °C.
Liquid phase, %mass Liquid phase, %mass Composition of the solid phase
BeSeO4 H2SeO4 BeSeO4 H2SeO4 36.22 - - BeSeO4.4H2O 32.69 5.35 58.59 1.78 “ - ” 30.29 8.80 62.60 2.01 “ - ” 25.85 15.93 63.30 2.01 “ - ” 19.99 30.03 62.48 3.13 “ - ” 15.00 46.50 64.58 3.32 “ - ” 11.71 53.77 54.49 12.57 “ - ” 11.58 60.56 65.11 3.05 “ - ” 10.93 68.50 60.01 9.26 “ - ” 10.81 71.94 61.48 7.51 “ - ”
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
144
4(ν
<!6
"ν
(!6
"
44(
-( -
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A-( ν
'.1<'
ν (*2 'ν
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Nν
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9 -((
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7727'+'ν(9
5
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''(1'2.7'ν<
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Fig. 5. Infrared spectra of beryllium sulfate hydrates in theregion of the internal vibrations of the SO
42- ions, BeO
4 skeleton
vibrations and water librations (a, BeSO4.4H
2O; b, BeSO
4.4D
2O
(ca 80% D2O); c, BeSO
4.2H
2O; d, BeSO
4.2D
2O (ca 60% D
2O); e,
BeSO4).
M. Georgiev, V. Karadjova, D. Marinova, D. Stoilova
145
ν' -
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Fig. 6. Infrared spectra of beryllium selenate hydrates in theregion of the internal vibrations of the SeO
42- ions, BeO
4 skeleton
vibrations and water librations (a, BeSeO4.4H
2O; b, BeSeO
4.4D
2O
(ca 80% D2O); c, BeSeO
4)
16821509
b
a
410
436
670
760
870
990
1133
1164
1236
440
530
770
855
880
2 000 1 600 1 200 800 400
c
Wavenumbe rs, cm-1
440
666703
913
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
146
Oν<ν
(J 9
!5"#
'!:5"#
<!5"#
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*<7'ν'P
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Fig. 7. Raman spectrum of BeSeO4.4H
2O
Fig. 9. Infrared bands of OH and OD stretches (matrix-isolatedHDO molecules) in BeSeO
4.4H
2O, BeSO
4.4H
2O and BeSO
4.2H
2O
(a, BeSO4.4H
2O; b, BeSO
4.2H
2O; c, BeSeO
4.4H
2O)
a33 80 29 40
31 30
23 60
22 30
31 84
b
29 5731 13
24 04
22 4423 23
3500 3000
c
Wavenumbers, cm-1
2400 2100
//
Fig. 8. Correlation diagram between Td point group, site
symmetry and factor group symmetry (SO4
2- ions and [Be(H2O)
4]
complex in BeSO44H
2O.
Td D2 D2d
point group site symmetry factor group symmetry
ν1(A1) A1 (R) A ν2(E) B1 (R)
A2 (inactive) B1 ν3(F) B2 (IR, Raman) B2 ν4(F) E (IR,Raman) B3
M. Georgiev, V. Karadjova, D. Marinova, D. Stoilova
147
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
148
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REFERENCES
'%F,-!"'.11.+' <
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Tz. Kotzeva, V. Stefanova, I. Gadjov
149
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 149-153
ANODIC POLARIZATION OF THE FeCuNiCoMn ALLOY IN SULPHURIC ACID
Tz. Kotzeva, V. Stefanova, I. Gadjov
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected]
ABSTRACT
! " #
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Received 05 September 2007
Accepted 12 January 2008
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
150
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Fig. 1. An overview of quenched sample from FeCuNiCoMnalloy: 1- basic phase; 2- intermediate phase; 3 - cooper droplets.
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E,V
vs
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E)
ia, mA.cm-2
0.5M; 1M H2SO
4, 298 K
0.5M; 1M H2SO
4, 323 K
Fig. 2. Effect of the concentration of sulphuric acid andtemperature on the anodic polarization of polymetallic alloy.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
152
0 50 100 150 200 250 300 350
0,5
0,4
0,3
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-0,2
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E, V
vs
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E)
ia, mA.cm-2
KC Ni Co Cu Fe
Calculated curve
0 50 100 150 200 250 300 350
0,5
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0,3
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0,1
0,0
-0,1
-0,2
-0,3
-0,4
-0,5
E,V
vs
(SC
E)
ia, mA.cm-2
KC Ni Co Cu Fe
Calculated curve
Fig. 3. Anodic polarization curves of PA and the pure metals in 0.5 M (a) and 1M (b) sulphuric acid at 298 K.
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ia, mA.cm-2
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Calculated curve
0 100 200 300 400 500 600 700 800
0,5
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KC Ni Co Cu Fe
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Fig. 4. Polarization curves of PA and the pure metals (Fe, Ni, Cu, Co) in 0.5 M (a) and 1M (b) sulphuric acid at 323 K.
Tz. Kotzeva, V. Stefanova, I. Gadjov
153
, 7 #
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REFERENCES
% > J3 L , A
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
154
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 154-158
VISUALIZATION OF AN ON-LINE CLASSIFICATION AND RECOGNITIONALGORITHM OF EMG SIGNALS
Cv. Kocev3, A. Zeghbib1, G. Tsenov2, L. Antonov3, V. Mladenov2, F. Palis1, N. Shoylev3
1 Otto-von-Guericke-Universität Magdeburg,
Institut für Elektrische Energiesysteme
39016 Magdeburg, Germany2 Department of Theoretical Electrical Engineering,
Technical University of Sofia,
8 Kl. Ohridski St., BG-1000 Sofia, Bulgaria3University of Chemical Technology and Metallurgy,
8 Kl. Ohridski, 1756 Sofia, Bulgaria
ABSTRACT
Received 05 November 2007
Accepted 12 January 2008
INTRODUCTION
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Cv. Kocev, A. Zeghbib, G. Tsenov, L. Antonov, V. Mladenov, F. Palis, N. Shoylev
155
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
156
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Cv. Kocev, A. Zeghbib, G. Tsenov, L. Antonov, V. Mladenov, F. Palis, N. Shoylev
157
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
158
Fig. 3. 1. Movement detection.
Fig. 3.2. Movement classification.
Acknowledgements! "##"$$$
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Y. Tsepkovskiy, L. Antonov, Cv. Kocev, F. Palis, N. Shoylev
159
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 159-164
DEVELOPMENT OF A 3D AND VRML VIRTUAL HAND MODELSFOR DIFFERENT MECHANICAL GRIPPER
Y. Tsepkovskiy1, L. Antonov2, Cv. Kocev2, F. Palis1, N. Shoylev2
1 Otto-von-Guericke-Universität Magdeburg,
Institut für Elektrische Energiesysteme
39016 Magdeburg, Germany2 University of Chemical Technology and Metallurgy,
8 Kl. Ohridski, 1756 Sofia, Bulgaria
ABSTRACT
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Received 05 Septenber 2007
Accepted 12 January 2008
INTRODUCTION
EXPERIMENTS
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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Fig. 2. Virtual Reality Block in Matlab.
Y. Tsepkovskiy, L. Antonov, Cv. Kocev, F. Palis, N. Shoylev
161
Fig. 3. 1. Simulink scheme of the 3D animation hand model.
Fig. 3.2. Switches for different type of mechanical hand gripper realization.
Fig. 4.1. Gripper for catching bodies with cylindrical shape. Fig. 4.2. Gripper for three fingers catch.
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
162
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Y. Tsepkovskiy, L. Antonov, Cv. Kocev, F. Palis, N. Shoylev
163
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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V. Slavov, I. Angelov, I. Slavova
165
Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008, 165-168
FORCED THREE-DIMENSIONAL NON-LINEAR OSCILLATIONS OF ARTICULATEDVEHICLE WITH MONAXIAL TRAILER, CAUSED BY WORK
OF THE INTERNAL-COMBUSTION MOTOR AND BY 3D DISTURBANCESFROM THE ROUGHNESS OF THE ROAD
V. Slavov1, I. Angelov2, I. Slavova2
1University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected] University - Sofia
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: [email protected], [email protected]
ABSTRACT
Received 05 September 2007
Accepted 12 January 2008
INTRODUCTION
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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V. Slavov, I. Angelov, I. Slavova
167
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Journal of the University of Chemical Technology and Metallurgy, 43, 1, 2008
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)134()3434()134()3434( .. ×××× ++ qBqM
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r
∑∑∑
∑∑
∑
∑
= = =
Ω
= =
−
=
−
=
+−++
++
+Ω+Ω−
Ω+++
+
++−−++
+
+++−++
=
n
tiP
kk
k
l
tik
k
t
t
kePiP
iP
hg
ekik
ik
hg
tehg
tehg
t
*kl
*Fk
QGHG
QGHG
BHMGMHMH
BGMHMGMG
ωσωβα
ωσωβα
ββα
ββα
α
α
,#%-
∗FkQ ∗
klQ ,-,6-(
( ) 42 rTrrr
Trr
Trrr MWVMWWMVV +−−−= βαg
;rTrr
Tr BWWBVV −+
( )
.;
;;
;242
Trr
Trrrrrrrr
Trr
Trrrrrrrr
rTrr
Trrr
Trr
Trrr
VWWVRRLH
WWVVLRLG
BWVMWVMWWMVV
+=−=
−=+=
+−−=
gh
hg
h αβ
RESULTS AND DISCUSSION
*
Fig. 2. Forced oscillations with respect to generalized coordinate q25
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CONCLUSIONS
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REFERENCES
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