Zinc sulphide and Cadmium sulphide core shell nanoparticles: The

influence of Cadmium content on bandgap, structural, optical and

electrical properties.
Uzma Jabeen, Syed Mujtaba Shah*,
Department Of Chemistry, Quaid-i-Azam University, Islamabad, 45320, Pakistan.

Corresponding author :
Email: smschem69@yahoo.com
Phone: 0092-51-90642205
Fax: 0092-51-90642241
Postal Address: Dr. Syed Mujtaba Shah, Assistant Professor of Chemistry
Department of Chemistry, Quaid-i-Azam University, Islamabad, 45320, Pakistan.

Abstract
Zinc sulphide, cadmium sulphide and their coreshell nanoparticals, (ZnS/CdS/ZnS) were
synthesized by wet chemical method. The structural, optical and electrical properties of the
nanoparticles were investigated using X-ray diffraction (XRD), energy dispersive X-ray
spectroscopy (EDX), scanning electron microscopy (SEM), UV-visible and photoluminescence
spectroscopy. Micro-structural

analysis

using

Scanning

Electron

Microscope

(SEM)

supplemented with EDAX were carried out for the samples to find grain size and chemical
composition. SEM study revealed that the nanoparticles were aggregated to form clusters. The
variation in band gap of ZnS by CdS doping was investigated using optical spectroscopy. A
significant bathochromic shift of absorption band was observed by increasing the cadmium
concentration in core shell assembly. In a similar fashion emission peak of ZnS nano composite
was also tuned in a visible region by increasing the concentration of cadmium. The specific
surface area of ZnS, CdS and core shell nanoparticles was calculated at different temperature
using BET method. Finally, electrical conductivity was worked out by measuring the resistance
of the nanomaterial (in pallets) pasted on microscopic glass. The conductivity of the material was
enhanced by increasing cadmium concentration.

Key words: ZnS nanoparticles, CdS nanoparticles, core shell, surface modification, lattice strain,
conductivity.

1. Introduction
Semiconducting nanoparticles such as metal sulphide and metal oxides are well known for their
outstanding physical and chemical properties, owing to their use in photo-optics, optoelectronics,
electroluminescence devices, bio imaging technologies, light emitting devices, catalysis, sensors,
and solar energy cells. [1-7].
Size, shape, surface area and band gap energy are the important parameters which decide the
fate of nanoparticles for a specific application. Decrease in size leads to the increase of specific
surface area and bandgap energy. This is related to the quantum size effect or quantum
confinement [8]. Large surface area of nanoparticles results in their high adsorption capacity and
catalytic activity.
Doping impurities into nanoparticles is an effective approach for tuning their electronic,
magnetic, structural and optical properties for various desired applications [9 18]. ZnS is an
important II-VI semiconductor with a direct and wide band gap of 3.66 eV. It is widely used in
photovoltaic devices, solar cells and field emission devices (FED) [19 - 22]. Cubic ZnS is an
attractive host semiconductor for doping on account of its stability, low cost, and low toxicity
[23- 26]. A number of metal ions, such as Mn 2+, Cu+, Pb2+, Cd2+ , Ag+, and Eu2+, have been
successfully doped into ZnS to produce photoluminescence or electroluminescence in different
regions of the visible spectrum[27- 33].
Surface coatings not only alter charge and reactivity of the materials but also enhance their
functional properties by the localization of the electron-hole pairs [34]. Recently the synthesis of
composite nanomaterials is one of the hottest research domain particularly core-shell
semiconducting nanoparticles wherein a low bandgap semiconductor is sandwitched between
two layers of large bandgap semiconductor [35-37]. Core-shell semiconductors are typically
classified as type-I or type-II, depending on the relative placement of conduction and valence
band edges. In the type-I, both the conduction and the valence band edges of one semiconductor
are positioned within the energy gap of the other semiconductor. In this case, an electron-hole
pair tends to confine in semiconductor with lower band gap, which provides the lowest energy
states for both electrons and holes. In the type-II, the lowest energy states for electrons and holes
are in different semiconductors [38]. These nanocomposite materials have widespread
3

application in solar photovoltaic devices, chemical and biological sensors, and optoelectronics
such as light-emitting devices and optical switches [39]. Though much work has been done on
the synthesis of such nanocomposite materials but detailed investigation of their properties is yet
to be explored. Owing to its low bandgap, stability and photo-sensitizibility [40] we chose CdS
as a core and ZnS as shell material.
The aim of this work is to synthesize ZnS, CdS, and ZnS/CdS/ZnS core shell nanoparticles and
investigate their optical and structural properties by sandwiching CdS nanoparticles between two
ZnS layers. The influence of varying the concentration of shell precursor, CdS between two ZnS
particles layers on the variation of bandgap, structural, optical and electrical properties is
thoroughly investigated in this report in order to check its feasibility in opto-electronics and
photocatalysis.

2. Experimental
2.1 Chemicals
Zinc acetate (Zn (CH3COO)22H2O) and sodium sulfide, analytical grade were purchased from
Sigma Aldrich and were used as received. Deionized water and absolute alcohol (Sigma Aldrich)
were used as medium for the synthesis.
2.2 Synthesis of ZnS nanoparticles: ZnS nanoparticles were synthesized by wet chemical
method described elsewhere with a slight modification [41]. The synthesis was carried out in
water/ethanol mixed solvent (50:50). Zinc acetate (Zn (CH 3COO)22H2O) and sodium sulfide
(Na2S3H2O) were used as a precursors . For the synthesis of ZnS nanoparticles, 1 M of zinc
acetate was dissolved in 100 ml of solvent (50 mL deionized water and 50 mL ethanol). An
equimolar solution of Na2S was added drop by drop to the solution of zinc acetate under
continuous magnetic stirring at 60 C until a homogenous solution was obtained. Thereafter the
solution was cooled to room temperature. After 60 min, a white precipitate was appeared. The
precipitatae was carefully settled down and the supernatant solvent was discarded. The
precipitate was washed with deionized water and ethanol several times to remove impurities.
Finally it was dried in oven at 120 C for 2 h before subjecting them to structural and optical
characterization.
4

2.3 Synthesis of CdS nanoparticles: CdS nanoparticles were also synthesized in water/ethanol
medium by wet chemical method [41]. Cadmium acetate (Cd (CH 3COO) 24H2O) and sodium
sulfide (Na2S3H2O) were used as precursors. In a typical experiment 0.2 M of cadmium acetate
was dissolved in 100 ml of solvent (water + ethanol, 50:50). An equimolar solution of Na2S was
added drop wise to the above solution under constant magnetic stirring at 60 C. After the
addition of Na2S solution, a yellow precipitate was appeared. The supernatant solvent was
discarded and the precipitate was washed thrice with deionized water and ethanol to remove
impurities. The nanoparticles were dried in oven at 120 C for 2 h and properly characterized.
2.4 Synthesis of ZnS/CdS/ZnS core-shell nanoparticles: In a typical experiment, 1 M of Zn
(CH3COO)22H2O was dissolved in 100 ml of distilled waterethanol matrix (equal volume) and
an equimolar solution of sodium sulfide in the same solvent was slowly added to it drop wise.
The mixture was continuously stirred at 60 C until a homogeneous white solution was obtained.
After 30 min, different concentrations of cadmium acetate solution (0.20.5 M in 100 ml distilled
waterethanol matrix) were added to the above solution drop by drop. Consequently the white
color was tuned into greenish yellow. It could be due to the formation of the ZnS/CdS in the
colloidal solution. In the subsequent step, 0.5 M solution of zinc acetate and equimolar solution
of sodium sulfide solution (prepared in the same matrix) was added to the above colloidal
solution drop by drop with continuous stirring until the solution was turned yellow. This
indicated the formation of ZnS/CdS/ZnS coreshell nanoparticles. The reaction was stopped and
the yellow precipitate was carefully settled at room temperature. The precipitate was washed
thrice with deionized water and freshly distilled ethanol. Thereafter the core-shell nanoparticles
were dried in oven at 120 C for 2 h [41] and subjected to different characterization techniques.
2.5 Characterization
UV-visible (Shimadzu 1601) and uorescence spectrophotometer (Perkin Elmer LS55) were
used to explore the optical properties ofbare and core shell nanoparticles nanoparticles. The
purity and crystalline nature of synthesized nanoparticles were confirmed by X-ray
diffraction measurements. Scanning electron microscope (JSM 6490) supplemented with
EDAX (6490(LA)) was used for knowing the morphology, size and composition of
nanocrystals. Surface area analyzer BET was used to calculate surface area of nanoparticles.

Conductivity measurements of the nanocomposite material were conducted using Keithley

2400 Source Meter.

3. Results and discussions

3.1 Optical studies and bandgap tuning
Figure 1A shows the characteristic UVvisible (UVVis) absorption spectra of ZnS and CdS
nanoparticles. These spectra have broad absorption bands centered at 316 and 426 nm
respectively.
UV-Vis absorption spectra of core shell nanoparticles (ZnS/CdS/ZnS) with different CdS content
(0.2- 0.5 M) are shown in Fig. 2B. The absorption edge of ZnS/CdS/ZnS core shells shows a red
shift step by step compared to ZnS (316 nm, Fig 1A) with the increasing thickness of CdS. This
is depicted by the bathochromic shift of the broad absorptions centered at 333, 360, 380 and 395
nm. This shift could be associated with the partial leakage of the electronic wave function of the
ZnS into the CdS layer. When a shell is formed on the surface of the core, the total size is larger
than that of the core. As both the conduction and the valence band of CdS are located within the
energy gap of the ZnS nanoparticles, the potential well of ZnS/CdS/ZnS becomes deeper than
that of the pure CdS nanoparticles while decreased with respect to ZnS and consequently the
absorption spectra shows a red-shift.

0.9
0.8

Absorbance (a.u.)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0

300

400

500

600

700

800

Wavelength (nm)

333nm

Absorbance (a.u.)

0.6
360nm

ZnS/CdS/ZnS
ZnS/CdS/ZnS
395nm ZnS/CdS/ZnS
ZnS/CdS/ZnS

Cd 0.2M at 333 nm
Cd 0.3M at 360 nm
Cd 0.4M at 380 nm
Cd 0.5M at 395 nm

0.4
380nm

0.2

0.0
300

400

500

600

700

800

Wavelength (nm)

(1A)

(1B)

Figure 1 (A) UV-vis absorption spectra of (A) bare ZnS and CdS nanoparticles (B) core-shell,
ZnS/CdS/ZnS nanopaticles with different CdS contents.

The UV-visible absorption studies play a vital role in estimating the optical band gaps using Tauc
relation. The optical band gap (Eg), was estimated from the extrapolation of the linear portion in
a plot of h versus (Ah)2, where A is the absorbance and h is the photon energy Ref. table 1). It
is observed that Eg in the bare ZnS and CdS nanomaterial is 3.58 eV and 2.6 eV respectively. For
the core shell nanoparticles ZnS/CdS/ZnS having 0.2 M concentration of cadmium, Eg is found
to decrease to 3 eV. Increasing CdS content beyond 0.2 M, Eg further decreases to 2.74, 2.55 and
2.44eV, in the case of cadmium concentration of 0.3, 0.4 and 0.5 M respectively. Figure 2 shows
the Tauc plot for the calculation of the band gaps of ZnS, CdS and core shell nanoparticles
having different Cd concentrations.

0.5

( h )2

0.4
0.3
0.2
0.1
0.0
2.0

2.4

2.8

3.2

3.6

4.0

4.4

4.8

Energy (eV)
Figure 2 Tauc plots for ZnS (dash), CdS (dot) and core shell nanoparticles, ZnS/CdS/ZnS, 0.2 M
CdS (dash dot) ZnS/CdS/ZnS, 0.3 M CdS ( dash dot dot) ZnS/CdS/ZnS, 0.4 M (short dash)
ZnS/CdS/ZnS, 0.5 M CdS (short dot).
Bandgaps, calculated from the above plots are summarized in table 1. These results show that
increasing CdS content in the core shell nanoparticles leads to decrease in the bandgap energy.
Thus CdS content plays a key role in engineering the bandgap and tuning it to the absorption in
visible region effectively.
8

Table 1. Optical band gaps of ZnS, CdS and core shell nanoparticles of different compositions.
Column 3 shows the decrease in bandgap with respect to ZnS.

Sample composition
ZnS
CdS
ZnS/CdS/ZnS Cd 0.2 M
ZnS/CdS/ZnS Cd 0.3 M
ZnS/CdS/ZnS Cd 0. 4 M
ZnS/CdS/ZnS Cd 0. 5 M

Band gap (eV)

Decrease with respect

3.58
2.6
3.0
2.74
2.56
2. 44

to ZnS (eV)
_
_
0.58
0.88
1.00
1.12

Figure 3 shows the fluorescence emission spectra of bare ZnS and core shell nanoparticles with
different CdS content obtained by exciting the nanomaterial at 316 nm. A characteristic broad
blue emission band at 425 nm further evidenced the synthesis of ZnS nanoparticles. The PL
spectra of ZnS/CdS/ZnS core shell nanoparticles excited at 316 nm show a broad blue-green
emission spreading up to 600 nm which could be ascribed to emergence of multiple emission
bands along with the blue emission of ZnS. These spectra give the impression to have been
deconvoluted into three different bands with peak maxima at ~ 445, 484 and 530 nm
respectively. The first emission is ascribed to the recombination of electron-hole pairs in zinc and
sulphur vacancies of zinc sulphide nanoparticles. The second and third peaks are presumed to
originate from the radiative recombination of carriers at surface trap states resulting from the
effect of cadmium sulphide at ZnS/CdS/ZnS interface. The intense PL emission at 425 nm is
significantly red shifted in the visible region for core shell nano composites [41]. This is in
conformity with the absorbance spectra (Ref. Fig 1 B).

Emission intensity (a.u.)

300
250
200

ZnS bare
ZnS/CdS/ZnS, CdS 0.3 M
ZnS/CdS/ZnS, CdS 0.4 M
ZnS/CdS/ZnS, CdS 0.5 M

425

447
485

150
100

531

50
400

450

500

550

Wavelength (nm)

Figure 3 Emission spectra of Zns bare (short dash), core shell nanoparticles with different CdS
content, ZnS/CdS/ZnS, CdS 0.3 M (solid), ZnS/CdS/ZnS, CdS 0.4 M (dot), ZnS/CdS/ZnS, CdS
0.5 M (short dot)
3.1 Morphological studies
The grain size, shape and surface morphology were investigated by Scanning Electron
Microscope (JSM 6490). SEM images of ZnS, CdS , ZnS/CdS/ZnS (Cd 0.2 M) and
ZnS/CdS/ZnS (Cd 0.5 M) nanoparticles with different magnifications are depicted in figure 4A,
4B, 4C and 4D respectively. SEM image of ZnS nanoparticles reveals that particle size is not
uniform and the particles form irregular shaped clusters. On the other hand CdS nanoparticles
have regular shapes and uniform sizes. Addition of CdS at low concentration (0.2 M) has a
marked effect on the clusters of ZnS. This makes the particle size uniform. At higher CdS
10

concentration (0.5 M) the clusters assumes more or less spherical appearance with uniform
particle size approximately.

(4A)

(4C)
Figure 4.

(4B)

(4D)

SEM Micrographs of, (4A) Zinc sulphide, (4B) Cadmium sulphide, (4C)

ZnS/CdS/ZnS (Cd 0.2M) and (4D) ZnS/CdS/ZnS (Cd 0.5M).

11

To investigate the chemical composition of ZnS, CdS and their core shell nanoparticles
ZnS/CdS/ZnS , the elemental analyses of samples were performed by Energy Dispersive X-ray
Spectrometer (6490(LA)). Figure 5(A), 5(B), 5(C) and 5(D) shows the EDS spectra of the
synthesized ZnS , CdS and core shell nanoparticles. The spectrum in Figure 8 (A), shows the
EDS spectrum of ZnS, it reveals the presence of Zn and S peaks confirming the formation of zinc
sulphide but some additional peaks of oxygen are also present. The presence of oxygen atom in
nanostructure could be due to the distilled water used in the synthesis. It is also observed that
sample contains higher percentage of Zinc (Zn) and less percentage of sulfur (S). The average
atomic percentage ratio of Zn:S is 31.12:18.36. Figure 5 (B) shows the EDS spectrum of CdS,
reveals the presence of Cd and S peaks confirming the formation of cadmium sulphide. Some
additional peaks of oxygen are also noticed (already interpreted). The average atomic percentage
ratio of Cd:S is 35.68:33.37.
The EDS patterns of ZnS/CdS/ZnS core shell nanoparticles with low and high concentration of
CdS shell thickness are shown in Figure 5 (C) and 5 (D) respectively. Figure 5 (C) shows the
EDS spectrum of ZnS/CdS/ZnS (Cd 0.2M). It shows peaks for Zn and S along with weak peaks
for Cd supporting the formation of CdS shell over ZnS core. The average atomic percentage ratio
of Zn:S:Cd is 28.94:25.53:6.24. Figure 5 (D) shows the EDS spectrum of ZnS/CdS/ZnS (Cd
0.5M). It has peaks for Zn and S along with weak peaks for Cd supporting the formation of CdS
shell over ZnS core. The average atomic percentage ratio of Zn:S:Cd is 19.08:19.15:11.52.

12

(a)

(b)

13

(c)

(d)
Figure 6 The EDX Spectra of synthesized (a) ZnS nanoparticles, (b) CdS nanoparticles (C)
,ZnS/CdS/ZnS (Cd 0.2 M) core shell nanoparticles and (d) ZnS/CdS/ZnS (Cd 0.5 M) core shell
nanoparticles.

Table 2 (a), (b), (c) and (d) gives the compositions of prepared sample of ZnS, CdS,
ZnS/CdS/ZnS (Cd 0.2M) and ZnS/CdS/ZnS (Cd 0.5M) respectively in weight and atomic
percentage.

14

(a)
(c)

(b)
(d)

3.2 Fourier transform infra-red spectroscopy

Figure 7 a, b and c shows the FTIR spectra of the synthesized ZnS, CdS and core shell
nanoparticles (ZnS/CdS/ZnS, Cd 0.3 M). FTIR spectra confirmed the purity and composition of
the samples. The FTIR spectra could be explained by the various peaks obtained by the samples.
The absorption peak in the range from 3600 to 3200 cm -1 corresponds to the OH group of water
adsorbed by the samples. The weak absorption band at 1627 to 1636 cm -1was attributed to the
CO2 adsorbed on the surface of the particles, which is a quite common for nanosized powder
with a high surface area [42]. Small peak near 634-638 cm -1 indicated the formation of Zn-S and
Cd-S bonds as this region is assigned to Metal-Sulphur bonds [43].FT-IR spectra of core shell

15

nanocomposites (figure 7c) is more similar to CdS nanomaterial than ZnS. These results show
that CdS effectively covers the ZnS core.

(a)

(b)

16

(c)

Figure 7

FT-IR spectra of (a) ZnS, (b) CdS and (c) core shell nanomaterials ZnS/CdS/ZnS (Cd,

0.3 M)

3.2 Surface area of nanoparticles

Surface area of samples was determined by Brunauer-Emmett- Teller (BET) mehod using
Quantachrome instruments (Model NOVA 2000 surface area). Before the specific surface area
of the sample is calculated, it is necessary to remove gases and vapours that may have become
physically adsorbed onto the surface after synthesis and during treatment, handling and storage.
If out gassing is not achieved, the specific surface area may be reduced or may be variable
because an appreciable area of the surface is covered with molecules of the previously adsorbed
gases or vapours. The outgassing conditions are critical for obtaining the required precision and
accuracy of specific surface area measurements.

17

BET surface area of samples heated at different temperatures starting from 150 C to 450 C is
presented in figure 8. All samples have similarly shaped hysteretic behaviors. The value of
surface area first increases (maximum at 250 C) and then decreases by increasing the heating
temperature. This result reveals that samples heated at 250 0C are more porous or have the
smallest particles size than the samples heated at other temperatures. The decrease in specific
surface area at high temperature may be attributed to the increase in grain size. On heating the
sample at high temperature (4500C), the particles become agglomerated which may lead to
decrease in the specific surface area.

Fig. 8 surface area (BET) for ZnS (1), CdS (2), ZnS/CdS/ZnS (Cd 0.2 M) (3),ZnS/CdS/ZnS (Cd
0.3 M) (4), ZnS/CdS/ZnS (Cd 0.4 M) (5) and ZnS/CdS/ ZnS (Cd 0.5M) (6) nanoparticles at
different temperatures.
The results of above plots have been summarized in table 3.

ZnS

1500C
36.58

BET surface area m2 g-1

2500C
3500C
56.82
43.55

4500C
22.32

CdS

65.29

79.55

68.903

51.66

ZnS/CdS/ZnS(Cd 0.2 M)
ZnS/CdS/ZnS (Cd 0.3 M)
ZnS/CdS/ZnS (Cd 0.4 M)

114.36
110.61
102.22

133.87
128.22
117.55

123.56
119.68
110.22

102.82
96.77
91.32

Samples

18

ZnS/CdS/ZnS (Cd 0.5 M)

93.97

112.21

104.92

89.301

Table 3. BET surface area of ZnS, CdS and ZnS/CdS/ZnS core shell nanoparticles at various
compositions and heating temperatures.

3.2 Electrical conductivity

ZnS, CdS and their core shell nanoparticles were also characterized in terms of electrical
conductivity. The data is presented in table 4. Electrical conductivity was tested by measuring the
resistance values using digital multimeter (Keithley 2401). This test is important to know the
movement of electrons in nanocrystallites. According to the band theory of solids, the process of
conduction depends on the number of electrons in the conduction band. [47]. Conductivity is
increased when electrons in valence band are supplied with external energy and excited into the
conduction band. The following two equations were used to calculate the conductivity of ZnS,
CdS and their core shell nanoparticles.

Where R is resistance (), l is length between 2 points (mm), and A is area of nanoparticle paste
onto glass substrate (m), is resistivity (mm) and is conductivity (-1m-1m).

Sample
ZnS
CdS
ZnS/CdS/ZnS Cd 0.2 M
ZnS/CdS/ZnS Cd 0.3 M
ZnS/CdS/ZnS Cd 0.4 M
ZnS/CdS/ZnS Cd 0.5 M

Resistance,
1.90E6
9.38E6
7.34E6
6.53E6
4. 43E6
2.99E6

Resistivity, m
35.94E3
78.54E3
61. 46E3
54.67E3
37.09E3
25.036E3

Conductivity, -1m-1
2.78E-5
1.27E-5
1.62E-5
1.82E-5
2.69E-5
3.99E-5

19

Table 4 . The average values of resistance, resistivity and conductivity of ZnS, CdS and their
core shell nanoparticles (ZnS/CdS/ZnS) nanoparticles at various Cd content.

The table shows that zinc sulphide has higher conductivity than cadmium sulphide but the the
addition of Cd at various concentrations has an appreciable effect on the conductivity of core
shell nanoparticles. Core shell nanoparticles at the lowest Cd content (0.2 M), though less
conducting than bare ZnS, has higher conductivity than bare CdS. Further increase of the
cadmium content make the core shell nanoparticles more conducting than both the bare ZnS and
CdS. At cadmium content of 0.5 M, conductivity raises to 3.99 10 -5 -1m-1 which is higher than
bare ZnS and CdS by 1.21 10-5 -1m-1 and 1.72 10-5 -1m-1 respectively.

Conclusion:

Zinc sulphide , cadmium sulphide and their core shell nanoparticles

were

successfully synthesized by chemical route. They were characterized by scanning electron

microscopy, electron diffraction X-ray analysis, fourier transform infra-red spectroscopy, UV-Vis
absorption, photoluminescence spectrophotometry and BET surface area analyzer. The structural,
optical and electrical properties of the bare ZnS, CdS and their core shell nanoparticles were
thoroughly investigated. The effect of cadmium content on the particle size and bandgap tuning
in the core shell nanoparticles was also studied. It was found that the change in the concentration
of Cd had a significant effect on the absorbance. The absorbance peak was progressively redshifted by increasing Cd content and consequently the bandgap was reduced from 3.58 eV (ZnS)
to 3 eV for the core shell nanoparticles (Cd, 0.2 M) which was further reduced to 2.44 eV when
the cadmium content was raised to 0.5 M. SEM showed that increasing the Cd content induced
uniformity in the particle size and led to spherical shaped clusters. EDX pattern gave evidences
of the presence of Zn, Cd and S in core shell nanoparticles approximately in the same ratio in
which they were mixed to synthesize the material. Specific surface area of the core shell
nanoparticles was found maximum at 250 C, by further rising the temperature it was decreased
due the agglomeration of the particles at high temperature. Electrical conductivity of the core
shell nanoparticles was progressively increased by rising Cd content. It attained a maximum
20

value of 3.99 10-5 -1m-1 at cadmium content of 0.5 M which was found higher than bare ZnS
and CdS by 1.21 10-5 -1m-1 and 1.72 10-5 -1m-1 respectively.

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