Synthesis, thermal study and some properties of Zn(II), Cd(II) and Pb(II) compounds with mono-, di- and trichloroacetates

Article abstract of DOI:10.1007/s10973-016-5940-6

New complexes with formulae: Zn(CClH₂COO)₂·2H₂O, Zn(CCl₂HCOO)₂·2H₂O, Zn(CCl₃COO)₂·2H₂O, Cd(CCl₂HCOO)₂·H₂O, Cd(CCl₃

Full text of DOI:10.1007/s10973-016-5940-6

J Therm Anal Calorim
DOI 10.1007/s10973-016-5940-6
Synthesis, thermal study and some properties of Zn(II), Cd(II)
and Pb(II) compounds with mono-, di- and trichloroacetates
1
A. Czylkowska1 A. Raducka1 P. Mierczynski
•
•
´
Received: 14 June 2016 / Accepted: 28 October 2016
Ó The Author(s) 2016. This article is published with open access at Springerlink.com
Abstract New
Zn(CClH2COO)2Á2H2O,
Zn(CCl3COO)2Á2H2O,
complexes
with
formulae:
medical analysis to remove proteins from blood or serum in
the determination of glucose. Sodium salt of trichloroacetic
acid is used in agriculture, as one of the herbicide. It is in
the fourth class of compounds known as damaging agents.
In the plastics industry, it is used as a solvent for plastics, in
metal industry to the surface treatment of metals, due to of
the corrosive properties [2, 3]. This acid is widely present
in the environment. It is characterized by very high sta-
bility. Their high solubility in water makes, that it occurs in
the rain, snows, ice, fog fresh and marine waters as well as
in the soil [4, 5].
Zn(CCl2HCOO)2Á2H2O,
Cd(CCl2HCOO)2ÁH2O,
Cd(CCl3COO)2Á2H2O and Pb(CCl3COO)2Á2H2O, were
prepared and characterized by chemical, elemental analysis
and IR spectroscopy. The nature of metal–ligand coordi-
nation was studied. They are small crystalline. The thermal
properties of compounds in the solid state were studied
using TG–DTG techniques under dynamic flowing air
atmosphere. Mass spectrometer was used to analyze prin-
cipal volatile thermal decomposition and fragmentation
products of Zn(CCl3COO)2Á2H2O evolved during pyrolysis
in dynamic flowing air and in argon atmosphere.
To the research were selected d-block metals and lead
(although it is metal of p-block). Lead and zinc are clas-
sified as non-ferrous metals. A common feature of the
selected elements is the ability to create different type of
complexes.
Keywords Metal(II) complexes Á Monochloroacetates Á
Dichloroacetates Á Trichloroacetates Á TG–DTG Á MS
study Á IR spectra
In literature there is a note about Zn(II) chloroacetate
and its complexes with nicotinamide and caffeine [6]. Also,
there is some information about Zn(II), Cd(II) and Pb(II)
with acetic acids [7–18].
Introduction
This paper investigates several solid compounds of Zn(II)
and Cd(II)with mono-, di-, or trichloroaceticacids and Pb(II)
with trichloroacetic acids (as the most common compound of
lead with chloroacetates, which is in the soil). Their stoi-
chiometric composition, nature of the metal–organic ligand
bond, molar conductivity in various solvents and thermal
behavior were studied. Thermal stability in air, information
about stages of pyrolysis, intermediate and final solid prod-
ucts of decomposition of investigated compounds are
described. In addition, for Zn(CCl3COO)2Á2H2O as an
example, volatile species emitted during thermal decompo-
sition in air and for comparison in argon atmosphere were
studied. This compound was chosen because it is important
for the environment.
The carboxylic acids are one of the most important organic
acids because of their application. They are starting com-
pounds for the synthesis of many derivatives. Substituents
of the carboxylic acids have an impact on acidity. A car-
boxylate group as a ligand can coordinate with metal ion
in various ways [1], making it interesting. The title
chloroacetic acid is widely used. It is used in medicine
since it has astringent and antiseptic properties, in the
& A. Czylkowska
agnieszka.czylkowska@p.lodz.pl
1
Institute of General and Ecological Chemistry, Technical
University of Lodz, Lodz, Poland
123

A. Czylkowska et al.
Table 1 Analytical data and molar conductivity in MeOH, DMF and DMSO for investigated compounds
Compound
Analysis:
found (calculated)/%
KM/X-1 cm2 mol-1
c = 1 9 10-3 mol L-1
;
M(II)
C
H
MeOH
41.4
DMF
DMSO
20.2
Zn(CClH2COO)2Á2H2O
Zn(CCl2HCOO)2Á2H2O
Cd(CCl2HCOO)2ÁH2O
Zn(CCl3COO)2Á2H2O
Cd(CCl3COO)2Á2H2O
Pb(CCl3COO)2Á2H2O
22.45
16.75
2.86
11.6
10.1
11.1
2.0
(22.65)
18.33
(16.66)
13.70
(2.80)
1.71
45.5
42.4
46.0
43.0
48.5
21.2
22.7
1.7
(18.30)
29.05
(13.45)
12.46
(1.69)
1.05
(29.10)
15.47
(12.44)
11.37
(1.04)
1.00
(15.34)
23.76
(11.27)
10.20
(0.95)
0.90
9.0
21.0
1.8
(23.78)
37.87
(10.15)
8.86
(0.85)
0.40
3.0
(37.69)
(8.74)
(0.37)
2000
1500
1000
500
0
10
30
40
50
60
20
70
80
90
2θ/°
Fig. 1 X-ray diffraction patterns of Pb(CCl3COO)2Á2H2O compound
Experimental
Methods and instruments
IR spectra were recorded with a NICOLETT 6700 Spec-
trometer (4000–400 cm-1 with accuracy of recording
1 cm-1) using KBr pellets. Molar conductance was mea-
sured on a conductivity meter of the OK-102/1 type
equipped with an OK-902 electrode at 25 0.5 °C, using
1 9 10-3 mol L-1 solutions of complexes in methanol,
dimethylformamide and dimethylsulfoxide. The thermal
properties of complexes in air were studied by TG–DTG
techniques in the range of temperature 25–1000 °C at a
heating rate of 10 °C min-1; TG and DTG curves were
recorded on Netzsch TG 209 apparatus in flowing dynamic
air atmosphere v = 20 mL min-1 using ceramic crucibles.
The mass spectra were measured on mass spectrometer
ThermoStar, Balzers (Germany), in the range of tempera-
ture 25–1000 °C at a heating rate 10 °C min-1 in flowing
Materials, synthesis and analysis
CClH2COOH, CCl2HCOOH and CCl3COOH were obtained
from Aldrich. Zinc(II) monochloroacetates, zinc(II)
dichloroacetates, zinc(II) trichloroacetates, cadmium(II)
dichloroacetes, cadmium(II) trichloroacetates and lead(II)
trichloroacetates were prepared by adding 2 mol L-1 mono-,
di- or trichloroacetic acid to freshly precipitated metal(II)
carbonates (in room temperature). After obtaining saturated
solutions, the excess of carbonates was filtered off. These
solutions were left to crystallize.
The contents of C and H in prepared compounds were
determinate by a Carlo-Erba analyzer with V2O5 as an
oxidizing agent; the metal(II) ions in obtained solutions
were determined by EDTA titration.
123

Synthesis, thermal study and some properties of Zn(II), Cd(II) and Pb(II) compounds with…
results were analyzed using the Powder Diffraction File
Table 2 Principal IR bands for CClH2COONa and for obtained
compound
[19].
CClH2COONa
[21]
Compound
Zn(CClH2COO)2Á2H2O
Assignments
Results and discussion
3005
2975
1603
1418
–
mas(CH2)
ms(CH2)
2360
1598
1434
1402
1388
1263
1249
1243
1197
1170
960
In the solid state, six new compounds with formulae:
mas(COO)
ms(COO)
Zn(CClH2COO)2Á2H2O,
Zn(CCl3COO)2Á2H2O,
Zn(CCl2HCOO)2Á2H2O,
Cd(CCl2HCOO)2ÁH2O,
Cd(CCl3COO)2Á2H2O and Pb(CCl3COO)2Á2H2O were
obtained. Unfortunately, obtained Cd(II) compound with
monochloroacetates has heterogeneous composition.
Therefore, further research was discontinued.
1399
1260
1251
m(CH2)
qt(CH2)
p(CH2)
1166
Table 1 presents results of the elemental and chemical
analysis of isolated compounds. They do not change their
stoichiometric composition in solid state. The analysis of
the power diffraction patterns of these compounds shows
that they are small crystalline. The most crystalline is
Pb(CCl3COO)2Á2H2O. Figure 1 presents, as an example,
X-ray diffraction pattern of lead(II) compound. Table 1
shows molar conductivities values for all investigated
compounds in solutions: MeOH, DMF and DMSO. All of
them in DMF and also Zn(CCl3COO)2Á2H2O and
Pb(CCl3COO)2Á2H2O in DMSO fall within the generally
acceptable range for non-electrolytes [20]. All compounds in
MeOH and Zn(CClH2COO)2Á2H2O, Zn(CCl2HCOO)2Á2H2O,
Cd(CCl2HCOO)2ÁH2O, Cd(CCl3COO)2Á2H2O in DMSO
display behaviors intermediate between those of non-elec-
trolytes and 1:1 electrolytes. Relatively not high molar
conductance shows that they dissociate only in limited
degree in these solutions.
932
926
769
682
185
m(CC)
935
qt(CH2)
788
m(CCl)
–
bas(CCOO)
196, 164
Dm = mas(COO) - ms(COO)
air and argon atmosphere v = 20 mL min-1 in ceramic
crucibles. The m/z values are given based on H, 12C, 16O
1
and 35Cl (additionally 13C and 18O in case of CO2), in the
range m/z: 1–120. The X-ray powder diffraction patterns of
synthesized complexes and final solid decomposition
products in air were recorded on D-5000 diffractometer
using Ni-filtered CuKa radiation. The measurements were
carried out in the range of 2h angles 2° – 80°. Obtained
Table 3 Principal IR bands for CCl2HCOONa and for obtained compounds
CCl2HCOONa [21]
2985
Compounds
Assignments
Zn(CCl2HCOO)2Á2H2O
Cd(CCl2HCOO)2.H2O
3012
2918
2850
1662
1652
1375
1338
1225
2995
2355
m(CH)
1640
1399
1624
mas(COO)
ms(COO)
m(CH)
1391
1324
–
1228
1218
1203
934
–
1194
918
d(CCOO)
m(CC)
954
813
823
804
mas(CCl2)
807
783
738
727
727
bas(CCOO)
710
669
241
324, 314, 287, 277
300, 233
Dm = mas(COO) - ms(COO)
123

A. Czylkowska et al.
Table 4 Principal IR bands for CCl3COONa and for obtained compounds
CCl3COONa [21]
Compounds
Assignments
Zn(CCl3COO)2Á2H2O
Cd(CCl3COO)2Á2H2O
Pb(CCl3COO)2Á2H2O
1671
1353
1670
1671
1656
1371
1344
929
1589
mas(COO)
ms(COO)
1361
1346
960
1392
1344
947
942
833
m(CC)
838
846
835
mas(CCl3)
829
749
757
744
746
762
ms(CCl3)
713
752
748
688
318
669
686
678
ms(CCl3)
324, 309
327, 312, 300, 285
245, 197
Dm = mas(COO)-ms(COO)
IR spectra
are determined based on the separation parameter
Dm = mas(COO)–ms(COO) [22–24]. In the investigated
compounds, the values of Dm (Dm \ DmNa) indicate mainly
bidentate chelating type of coordination of carboxylate
groups.
Tables 2–4 show absorption bands in the region
characteristic for mono- di- and trichloroacetates. For all
compounds, the vibration of mas(COO) and ms(COO) are
identified as the strong bands. The criterions of possible
coordination of carboxylate groups in obtained compounds
In all cases, the bands ms(COO) are split into two.
Additionally,
for
Zn(CCl2HCOO)2Á2H2O
and
Table 5 Thermal decomposition data in dynamic air atmosphere of obtained compounds
No.
Compound
Range of decomposition/°C DTG peaks/°C Mass loss/%
Found Calc
Intermediate and residue solid products
(I)
Zn(CClH2COO)2Á2H2O
50–125
125–300
300–340
340–525
50–175
75
2.70
3.12
Zn(CClH2COO)2Á1.5H2O
250
39.30
39.55 Zn(CClH2COO)0.5ÁCl1.5
5.04
320
4.90
Zn(CClH2COO)0.25ÁCl1.75
b
475
42.30a
7.30
–
(II)
Zn(CCl2HCOO)2Á2H2O
75
7.56
Zn(CCl2HCOO)2Á0.5H2O
175–275
325–500
50–140
220
48.00
43.00a
4.00
47.82 Zn(CCl2HCOO)0.25ÁCl1.75
–
b
470
(III) Cd(CCl2HCOO)2ÁH2O
70
4.66
Cd(CCl2HCOO)2
140–200
200–240
240–660
50–90
125, 160
180, 210, 230
320, 540, 600
75
35.50
35.91 Cd(CCl2HCOO)0.5ÁCl1.5
11.98 CdCl2
12.00
45.00a 14.21 CdO
(IV) Zn(CCl3COO)2Á2H2O
8.50
8.46
Zn(CCl3COO)2
170–215
350–475
50–145
190, 200
470
59.50
30.00a
34.50
27.00
59.65 ZnCl2
b
–
(V)
Cd(CCl3COO)2Á2H2O
125
34.44 Cd(CCl3COO)ÁCl
26.82 CdCl2
145–190
450–650
100–155
155–180
170
625
37.00a 11.60 CdO
(VI) Pb(CCl3COO)2Á2H2O
140, 145
165
39.50
20.50
39.86 Pb(CCl3COO)0.5ÁCl1.5
20.84 PbO
a
The greater than expected mass loss is connected with the formation of volatile products containing metal(II) ions
Unidentified final solid product of thermal decomposition
b
123

Synthesis, thermal study and some properties of Zn(II), Cd(II) and Pb(II) compounds with…
Fig. 2 TG and DTG curves of
thermal decomposition of
(a)
DTG/% min–1
5
TG/%
a Zn(CClH2COO)2Á2H2O
100
recorded in air atmosphere;
mass sample 9.50 mg;
DTG
0
b Zn(CCl2HCOO)2Á2H2O
80
60
recorded in air atmosphere;
mass sample 10.64 mg;
c Zn(CCl3COO)2Á2H2O
recorded in air atmosphere;
mass sample 7.13 mg
–5
–10
–15
40
20
–20
TG
–25
700
400
200
300
600
100
500
Temperature/°C
(b)
TG/%
DTG/% min–1
5
100
DTG
0
80
60
40
20
0
–5
–10
–15
TG
500
100
300
400
600
700
200
Temperature/°C
(c)
TG/%
DTG/% min–1
100
80
60
40
20
0
DTG
0
–10
–20
–30
–40
–50
TG
–60
700
100
200
300
400
500
600
Temperature/°C
123

A. Czylkowska et al.
Fig. 3 TG and DTG curves of
thermal decomposition of
Cd(CCl2HCOO)2ÁH2O recorded
in air atmosphere; mass sample
11.56 mg
DTG/% min–1
2
TG/%
100
DTG
0
80
60
40
20
0
–2
–4
–6
–8
–10
–12
TG
–14
400
600
700
400
200
300
100
Temperature/°C
Cd(CCl3COO)2Á2H2O compounds appears also separation
of mas(COO) band. Based on these data, we can conclude
about the different coordination of organic ligands in one
compounds, as well as, about formation of non-completely
equivalent bands between metal(II)-carboxylate groups
[25, 26].
They were also confirmed by the IR spectra of sinters. In
the sinters (prepared during heating of complexes up to
temperatures defined from TG curves), the vibration modes
of chloroacetates were analyzed as well as the presence of
anions Cl- was also stated. All Zn(II) and Cd(II) com-
pounds are stable up to 50 °C. Only Pb(CCl3COO)2Á2H2O
starts to decompose at 100 °C.
The compound of Zn(CClH2COO)2Á2H2O loses 0.5 mol
of water in a first stage of decomposition (50–125 °C);
mass founded 2.70% and calculated 3.12%. Further dehy-
dration process is accompanied by partial destruction of
monochloroacetates. In the ranges of temperature: 125–300
and 300–340 °C intermediate species Zn(CClH2COO)0.5Cl1.5
and Zn(CClH2COO)0.25Cl1.75 are created. Next, total
decomposition of monochloroacetates takes place. Between
340 and 525 °C high mass loss appears (42.30%), which is
probably associated with the formation of volatile decom-
position products containing zinc.
In addition, a broad band in the water stretching region
(ca 3450–3350 cm-1) appear for all described complexes.
Thermal decomposition
Thermal decomposition of analyzed compounds in air is a
multistage process. The solid intermediate products of
pyrolysis were determined from TG and DTG curves. The
thermal decomposition data are collected in Table 5.
Figures 2–5 present the thermoanalytical curves of
obtained complexes. From TG and DTG curves the solid
intermediate products of decomposition were determined.
Fig. 4 TG and DTG curves of
thermal decomposition of
DTG/% min–1
TG/%
DTG
0
100
Cd(CCl3COO)2Á2H2O recorded
in air atmosphere; mass sample
7.05 mg
–2
80
–4
–6
60
40
20
0
–8
–10
–12
–14
–16
TG
–18
400
500
600
700
300
200
100
Temperature/°C
123

Synthesis, thermal study and some properties of Zn(II), Cd(II) and Pb(II) compounds with…
Fig. 5 TG and DTG curves of
thermal decomposition of
DTG/% min–1
5
TG/%
Pb(CCl3COO)2Á2H2O recorded
100
in air atmosphere; mass sample
11.65 mg
DTG
0
90
–5
80
70
–10
–15
–20
–25
–30
–35
60
50
TG
40
30
20
400
100
150
200
250
300
350
50
Temperature/°C
Dehydration of Zn(CCl2HCOO)2Á2H2O is in two steps.
In the range 50–175 °C one and half water molecules are
released. Zn(CCl2HCOO)2Á0.5H2O species are stable up to
175 °C. When the temperature rises on TG curves is
observed the biggest mass loss (found 48.00%, calculated
47.82%), which is associated with further dehydration and
partial combustion of organic ligands (175–275 °C). In the
temperature range 325–500 °C volatile products containing
zinc appear.
Compound of Pb(II) starts to decompose at 100 °C. On
TG curve appears rapid mass loss (found 39.50%, calcu-
lated 39.86%). Such a decrease in mass is linked with
dehydration, and partial decomposition of carboxylates,
Pb(CCl3COO)0.5Cl1.5, occurs. Above 180 °C PbO forms.
MS study
Mass study was used to analyze the principal volatile
products evolved during the thermal decomposition and
fragmentation processes only for Zn(CCl3COO)2Á2H2O
compound. The determination was carried out in dynamic
air and argon atmospheres.
The Cd(CCl2HCOO)2ÁH2O losses 1 mol of water above
50 °C. Next, in the interval 140–200 °C partial destruction
of dichloroacetates takes place and forms intermediate
specie type Cd(CCl2HCOO)0.5Cl1.5. The TG curve shows a
rapid mass loss between 200 and 240 °C as a result of total
decomposition of organic ligands (CdCl2 is formed). In the
range 240–660 °C CdO is created. The mass loss calcu-
lated is 14.21%, but founded is 45.00%. This is probably
related with the formation of volatile products with
cadmium.
MS study in air
For Zn(CCl3COO)2Á2H2O major maxima for ion currents
are observed in temperature range 190–220 °C. For OH?
and H2O? (m/z = 17, 18), there is one peak around 85 °C
which is connected with the dehydration of zinc(II) com-
pound. When temperature rises, several gaseous products
Thermolysis of Zn(CCl3COO)2Á2H2O starts with the
dehydration. Zinc compound losses two water molecules in
one stage (50–90 °C). When the temperature rises,
decomposition of organic ligands appears and ZnCl2 exists.
It is accompanied by a high mass loss on TG curve (found
59.50%, calculated 59.65%). When the temperature rises
(350–475 °C) volatile products containing zinc are formed.
Thermal decomposition of Cd(CCl3COO)2Á2H2O begins
at 50 °C. On TG curve is recorded a high mass loss asso-
ciate with dehydration and partial destruction of organic
ligands (intermediate specie Cd(CCl3COO)Cl is formed).
Increasing temperature causes further degradation and
creates CdCl2 (145–190 °C). After this process volatile
products containing cadmium are emitted. Horizontal mass
level for CdO starts above 650 °C.
?
start to liberate. The profiles of CO2 (m/z = 44, 45)
exhibit very intensity maximum at 195 °C. At the same
temperature is also emitted C? with m/z = 12. These ion
signals (C?, CO2?) also have the same intensity and
similar profiles. The mass spectrometer detected also many
fragments containing chlorine with m/z = 35 (Cl?), 47
(CCl?), 70 (CCl2?), 82 (CCl2?), 117 (CCl3?). The chlorine
species appear between 190 and 220 °C. These molecular
ions have the main peaks in the temperature close to evo-
lution of carbon and dioxide. This proves a one-step
destruction of trichloroacetates. Further small peaks of
gaseous products containing chlorine (very low intensities
of ion currents) indicate the combustion of organic ligands.
123

A. Czylkowska et al.
(a)
7.00E-13
1
6.00E-13
5.00E-13
4.00E-13
3.00E-13
2.00E-13
1.00E-13
0.00E+00
1
2
3
3
4
2
4
600
200
400
500
300
Tempetature/°C
(b)
2.50E-11
2.00E-11
1.50E-11
1.00E-11
5.00E-12
0.00E+00
1
2
200
300
500
600
400
Tempetature/°C
Fig. 6 Selected ion currents detected by the MS spectra for
Zn(CCl3COO)2Á2H2O compound in air, mass sample 16.85 mg:
a m/z: 1–35 (Cl?), 2–70 (Cl2?), 3–82 (CCl2?), 4–117 (CCl?3 ) with
sensitivity of ion current: E-13 [A]. b m/z: 1–12 (C?), 2–44 (CO2?)
with sensitivity of ion current: E-11 [A]
The evaluation of all gaseous products finishes at ca
600 °C. Figure 6 presents as an example some ion currents
vs temperature.
and CO?2 (m/z = 44) have centers at 210 °C. The profile of
C? (m/z = 12) with very low intensity has a maximum at
ca. 240 °C. These facts suggest decomposition and oxi-
dization of organic ligands and the burning of the organic
residues. The major ion signals containing chloride with
m/z = 35, 47, 70 and 82 (Cl?, CCl?, Cl2?, CCl2?) have
centers between 200 and 240 °C. Additionally, the strong
peaks of O? and O?2 (m/z = 16 and 32) were monitored at
200 °C and at 220 °C, respectively. Thermolysis of
Zn(CCl3COO)2Á2H2O is one-stage in argon atmosphere.
MS study in argon
In inert atmosphere the ion currents appear in the range
200–240 °C. The peaks of H2O? (m/z = 18) and OH?
(m/z = 17) are connected with dehydration and occur at
about 200 °C. The ion signal intensities of CO? (m/z = 28)
123

Synthesis, thermal study and some properties of Zn(II), Cd(II) and Pb(II) compounds with…
(a)
2.50E-06
1
2.00E-06
1.50E-06
2
1.00E-06
5.00E-07
0.00E+00
400
500
600
200
300
Tempetature/°C
(b)
1.20E-07
1
1.00E-07
8.00E-08
6.00E-08
4.00E-08
2.00E-08
0.00E+00
3
2
4
600
500
300
400
200
Tempetature/°C
Fig. 7 Selected ion currents detected by the MS spectra for
Zn(CCl3COO)2Á2H2O compound in argon, mass sample 15.15 mg:
a m/z: 1–28 (CO?), 2–44 (CO2?) with sensitivity of ion current:
E-6 [A]. b m/z: 1–35 (Cl?), 2–47 (CCl?), 3–70 (Cl2?), 4–82 (CCl?2 )
with sensitivity of ion current: E-7 [A]
The process of dehydration is connected with the decom-
position of organic ligands. It was confirmed by emission
of gaseous products. As an example, Fig. 7 shows some ion
currents vs temperature.
Cd(CCl3COO)2Á2H2O and Pb(CCl3COO)2Á2H2O were
obtained. Described in [6] compound of zinc with
monochloroacetates also contains two water molecules.
Most zinc and cadmium acetates were obtained as dihy-
`
¨
drated compounds [7–10, 12, 13, 16]. Only Gyoryova and
Balek [17] synthesized zinc acetate with formulae
Zn(CH3COO)2Á2.5H2O.
Conclusions
The IR spectra of the synthesized compounds show, that
all carboxylate groups from chloroacetate ligands coordi-
nate with metal(II) atoms. Infrared spectra give us the
information about various types of organic ligands bonds.
All obtained compounds are stable at room temperature.
During heating they decompose progressively. They start
From the system: M(II)–RCOOH–H2O (where M(II) = Zn,
Cd, Pb; RCOOH = CClH2COOH, CCl2HCOOH and
CCl3COOH) six new compounds with stoichiometry:
Zn(CClH2COO)2Á2H2O,
Zn(CCl3COO)2Á2H2O,
Zn(CCl2HCOO)2Á2H2O,
Cd(CCl2HCOO)2ÁH2O,
123

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Mass Spectrom.
In case of zinc(II) and cadmium(II) chloroacetates for-
mation of volatile species containing metal(II) ions take
place. A similar phenomenon has been described in the
literature [8], where the authors recorded higher than
expected final mass loss. It has been attributed the forma-
tion of volatile compounds containing metal(II).
Mass study was used to analyze the principal volatile
thermal decomposition and fragmentation products in air
and in argon of Zn(CCl3COO)2Á2H2O. Relative, the most
species are detected in temperature ranges 190–220 °C (in
air) and 200–240 °C (in argon). In air and argon atmo-
sphere were observed different levels of intensity evolving
molecular ions with m/z = 12 and 44 (C? and CO2?). In air
was not observed presence of CO?. In both atmospheres
some fragments containing chlorine (Cl?, CCl?, Cl2?,
CCl?2 and CCl?3 ) were detected. These molecular ions were
not observed by the authors [6, 17].
The results described in this paper complete existing
knowledge of metal(II) compounds with halogenoacetates.
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16. Szunyogova E, Mudronova D, Gyoryova K, Nemcova R,
Acknowledgements We thank students M. Staniaszek and A. Ste˛-
´
pien for participation part of this work.
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Kovarova J, Piknova-Findorakova L. The physicochemical and
biological properties of zinc(II) complexes. J Therm Anal
Calorim. 2007;2:355–61.
Open Access This article is distributed under the terms of the
Creative Commons Attribution 4.0 International License (http://crea
tivecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.
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¨
17. Gyoryova K, Balek V. Thermal stability of new zinc acetate-
based complex compounds. J Therm Anal. 1993;40:519–32.
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solvents for the characterisation of coordination compounds.
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