1 Correction to the thermodynamic calculation by Ofudje et al.

(2023)

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2 Xueyong Zhou*, Xin Yu, Rehanguli Maimaitiniyazi, Ting Yue

3 School of Life Science, Shanxi Engineering Research Center of Microbial Application

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4 Technologies, Shanxi Normal University, Shanxi Taiyuan 030000, China

5 ∗Corresponding author. E-mail address: zhouxueyongts@163.com

6 ABSTRACT：This comment discussed the calculation of thermodynamic parameters

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7 in the paper of Ofudje et al. (2023). Although it is a highly academic paper, the

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8 thermodynamic parameters of Gibbs free energy change (ΔGo), enthalpy change

9 (ΔHo) and entropy change (ΔSo) of the adsorption of Cd2+ onto CHAp surface need to
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10 be corrected due to an incorrect calculation. The root reason for errors in Ofudje et
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11 al.’s paper is that the units of thermodynamic parameters are confused. In order to

12 obtain the correct results of thermodynamic parameters, the values of ΔG°, ΔH°, and

13 ΔS° were recalculated by using the original KD. By comparing the revised and the
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14 original Table, it is easy for the reader to know where the problem lies. As a research

paper, authors should not only demonstrate the novelty of their research, but also
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15

16 provide accurate results. This comment can improve the quality of paper writing and

17 avoid the misuse and propagation of the incorrect units in the area of adsorption
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18 thermodynamics.

19 Keywords: Thermodynamic parameters; Units; Calculation; Correction

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20 1. Introduction

21 Recently, Ofudje et al. (2023) published the paper entitled “Adsorption of Cd2+
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22 onto apatite surface: Equilibrium, kinetics and thermodynamic studies” in Heliyon 9

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4502863
 23 (2023) e12971[1]. There is no doubt that it is a highly academic paper. Their results

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24 showed that the chemically synthesized apatite (CHAp) could be an excellent

25 adsorbent for the elimination of Cd2+ in bioremediation applications. However, the

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26 thermodynamic parameters of Gibbs free energy change (ΔGo), enthalpy change

27 (ΔHo) and entropy change (ΔSo) of the adsorption of Cd2+ onto CHAp surface need to

28 be corrected due to an incorrect calculation.

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29 In Section 2.12. Thermodynamic studies, the thermodynamic parameters were

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30 determined by the following equations:

31
G o   RT ln K D
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S o H o
ln K D  
32 R RT (15)
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33 where in above Eqs., ΔGo, ΔHo and ΔSo are Gibbs free energy change (J/mol),

34 enthalpy change (J/mol) and entropy change (J/mol ⋅ K), respectively; R is the
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35 universal gas constant, 8.314 J/(mol⋅K); T is the absolute temperature, K; KD is the

36 standard equilibrium constant which is temperature dependent (dimensionless)[2-5].

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37 The values of thermodynamic parameters (ΔGo, ΔHo, and ΔSo) were listed in Table 4.

38 We found that the thermodynamic parameters in Table 4 were incorrect. As an

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39 example, looks at the Cd2+ adsorption by CHAp at 298K. In this case, the value of

40 ΔG° was computed as follows:

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41 ΔG°=-RTlnKD=-(8.314 J mol-1 K-1)×(298K)×ln(1.0028)=-6.928 (J/mol)

42 The calculation result was different from that in Table 4. The ΔG° calculated by
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43 Ofudje et al. for Cd2+ adsorption onto CHAp surface at 298K is -5.937 kJ/mol, i.e.,

44 -5937 J/mol, which is 857 times higher than our calculations. Therefore, the
2

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4502863
 45 thermodynamic parameters in Table 4 were incorrect.

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46 Table 4

47 Thermodynamic constants for Cd2+ adsorption by CHAp.

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T (K) KD ΔGo (kJ/mol) ΔH o (kJ/mol) ΔSo (KJ/mol) R2

298 1.0028 -5.937 175.591 0.610 0.968

303 1.0035 -8.817

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308 1.0044 -11.261

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313 1.0064 -16.656

318 1.0072 -20.035

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48 2. Correction to the thermodynamic calculation
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49 The root reason for errors in Ofudje et al.’s paper is that the units of

50 thermodynamic parameters are confused. In order to obtain the correct results of

51 thermodynamic parameters, the values of ΔG°, ΔH°, and ΔS° were recalculated by
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52 using KD provided in Table 4. The revised results were shown in Fig. 1 and Table 5.
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0.008

0.007

0.006
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0.005
LnKD

0.004

0.003
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0.002

0.001

0
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
1/T (K-1)
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53

54 Fig.1. Linear plot of lnKD vs. 1/T for the adsorption of Cd2+ at different temperatures

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 55 Table 5

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56 Thermodynamic constants for Cd2+ adsorption by CHAp.

T (K) KD ΔGo (J/mol) ΔHo (J/mol) ΔSo (J/(mol K)) R2

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298 1.0028 -6.928 183.07 0.6352 0.9635

303 1.0035 -8.802

308 1.0044 -11.242

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313 1.0064 -16.602

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318 1.0072 -18.968

57 3. Conclusions er
58 Ofudje et al.’s paper is of high academic value, however, errors in thermodynamic
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59 calculations should be corrected. As a research paper, authors should not only

60 demonstrate the novelty of their research, but also provide accurate results. We hope

61 that this comment can improve the quality of paper writing and avoid the misuse and
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62 propagation of the incorrect units in the area of adsorption thermodynamics.

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63 Author contribution statement

64 Xueyong Zhou: Conceived and designed the paper; Wrote the paper.
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65 Xin Yu: Analyzed and interpreted the data; Calculations.

66 Rehanguli Maimaitiniyazi: Analysis tools or data; Calculations.

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67 Ting Yue: Analyzed and interpreted the data; Plotted using the data.

68 Acknowledgements

69 The research is funded by the National Natural Science Foundation of China (No.
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70 31971551)，the project for Local Science and Technology Development Guided by

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4502863
 71 the Central Government in Shanxi Province, China (YDZJSX2022A055) ， the

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72 Graduate Education Innovation Project of Shanxi Normal University (2022XSY006)

73 and the Graduate Education Innovation Project of Shanxi Province (2022Y485).

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74 Reference

75 [1] E.A. Ofudje, E.F. Sodiya, O.S. Olanrele, F. Akinwunmi, Adsorption of Cd2+ onto

76 apatite surface: Equilibrium, kinetics and thermodynamic studies. Heliyon 9 (2023)

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77 e12971.

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78 [2] N.S. Ali, N.M. Jabbar, S.M. Alardhi, H. Sh. Majdi, T.M. Albayati, Adsorption of

79 methyl violet dye onto a prepared bio-adsorbent from date seeds: isotherm,
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80 kinetics, and thermodynamic studies. Heliyon 8 (2022) e10276.
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81 [3] X. Zhou, Comment on the thermodynamic calculation using the non-standard

82 equilibrium constant re Jemutai-Kimosop et al. (2020) and Conde-Cid et al. (2019).

83 Environ. Res. 187 (2020) 109610.

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84 [4] X.Y. Zhou, X. Zhou, The Unit problem in the thermodynamic calculation of

adsorption using the Langmuir equation. Chem. Eng. Comm., 201 (2014)
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85

86 1459-1467.

87 [5] X. Zhou, H. Liu, J. Hao. How to calculate the thermodynamic equilibrium

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88 constant using the Langmuir equation. Adsorpt. Sci. Technol. 30 (2012) 647-649.
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4502863