嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

引用本文: 李向红, 谢小光. 嘧啶衍生物对钢在盐酸溶液中的缓蚀作用[J]. 物理化学学报, 2013, 29(10): 2221-2231. doi: 10.3866/PKU.WHXB201307301 shu

Citation: LI Xiang-Hong, XIE Xiao-Guang. Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid Solution[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2221-2231. doi: 10.3866/PKU.WHXB201307301 shu

嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

李向红 ^1,2, ,
谢小光 ^1,

基金项目:
国家自然科学基金(51361027)资助项目 (51361027)

摘要:

采用失重法、动电位极化曲线、电化学阻抗谱(EIS)、量子化学计算研究了两种嘧啶衍生物(2-羟基嘧啶(HP)和2-巯基嘧啶(MP))在1.0-5.0 mol·L^-1 HCl溶液中对冷轧钢(CRS)的缓蚀作用. 结果表明: HP和MP在1.0 mol·L^-1 HCl溶液中对冷轧钢具有良好的缓蚀作用, 且在钢表面的吸附符合Langmuir吸附等温式. 缓蚀率随缓蚀剂浓度的增加而增大, 但随盐酸浓度的增加而减小.求出了相应的吸附热力学参数(吸附平衡常数(K),吸附自由能(ΔG⁰))和腐蚀动力学参数(表观活化能(E_a)、指前因子(A)、腐蚀速率常数(k)、动力学常数(B)), 并根据这些参数讨论了缓蚀作用机理. 动电位极化曲线表明, MP和HP均为混合抑制型缓蚀剂; EIS谱呈单一容抗弧,电荷转移电阻随缓蚀剂浓度的增加而增大. 两种嘧啶化合物的缓蚀率排序为MP>HP. 量子化学计算结果表明,MP比HP更具吸附活性,缓蚀性能的理论计算和实验结果相一致.

关键词:

English

Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid Solution

LI Xiang-Hong ^1,2, ,
XIE Xiao-Guang ^1,

1.
1 School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. China;
2 Faculty of Science, Southwest Forestry University, Kunming 650224, P. R. China
Received Date: 22 May 2013
Available Online: 26 September 2013
Fund Project:
国家自然科学基金(51361027)资助项目

Abstract:

The inhibition effect of two pyrimidine derivatives, 2- hydroxypyrimidine (HP) and 2- mercaptopyrimidine (MP), on the corrosion of cold rolled steel (CRS) in 1.0-5.0 mol·L^-1 HCl is investigated by mass loss, potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and quantum chemical calculations. The results show that HP and MP are both od inhibitors of corrosion of CRS in 1.0 mol·L^-1 HCl solution. The adsorption of these inhibitors onto the CRS surface obeys the Langmuir adsorption isotherm. Inhibition efficiency increases with inhibitor concentration, and decreases with hydrochloric acid concentration. The thermodynamic parameters of adsorption (adsorption equilibrium constant (K) and adsorption free energy (ΔG⁰)) and kinetic parameters of corrosion (apparent activation energy (E_a), pre-exponential factor (A), corrosion rate constant (k), and kinetic reaction constant (B)) are also calculated. Based on these parameters, the mechanism of inhibition is discussed. Potentiodynamic polarization curves show that HP and MP act as mixed-type inhibitors. EIS exhibit one capacitive loop, and the charge transfer resistance increases with inhibitor concentration. The results of quantum chemical calculations indicate that MP exhibits higher adsorptive ability than HP, which is in od agreement with the experimental data.

Key words:

1. [1]
  
  (1) Li, X. H.; Deng, S. D.; Fu, H. Acta Phys. -Chim. Sin. 2011, 27,2841. [李向红, 邓书端,付惠.物理化学学报, 2011, 27,2841.] doi: 10.3866/PKU.WHXB20112841
  (1) Li, X. H.; Deng, S. D.; Fu, H. Acta Phys. -Chim. Sin. 2011, 27,2841. [李向红, 邓书端,付惠.物理化学学报, 2011, 27,2841.] doi: 10.3866/PKU.WHXB20112841
2. [2]
  (2) Bentiss, F.; Traisnel, M.; Gengembre, L.; Lagrenée, M. Appl. Surf. Sci. 1999, 152, 237. doi: 10.1016/S0169-4332(99)00322-0(2) Bentiss, F.; Traisnel, M.; Gengembre, L.; Lagrenée, M. Appl. Surf. Sci. 1999, 152, 237. doi: 10.1016/S0169-4332(99)00322-0
3. [3]
  (3) Yan, Y.; Li, W. H.; Cai, L. K.; Hou, B. R. Electrochim. Acta2008, 53, 5953. doi: 10.1016/j.electacta.2008.03.065(3) Yan, Y.; Li, W. H.; Cai, L. K.; Hou, B. R. Electrochim. Acta2008, 53, 5953. doi: 10.1016/j.electacta.2008.03.065
4. [4]
  (4) Wang, L. J. Yunnan Univ. 2001, 23, 203. [王林.云南大学学报, 2001, 23, 203.](4) Wang, L. J. Yunnan Univ. 2001, 23, 203. [王林.云南大学学报, 2001, 23, 203.]
5. [5]
  (5) Monticell, C.; Brunoro, G.; Frignani, A. J. Electrochem. Soc.1992, 139, 706.(5) Monticell, C.; Brunoro, G.; Frignani, A. J. Electrochem. Soc.1992, 139, 706.
6. [6]
  (6) Lin, Z. H.; Wang, F. C.; Tian, Z. Q. Acta Phys. -Chim. Sin. 1992,8, 87. [林仲华, 王逢春,田中群. 物理化学学报, 1992, 8, 87.]doi: 10.3866/PKU.WHXB19920116(6) Lin, Z. H.; Wang, F. C.; Tian, Z. Q. Acta Phys. -Chim. Sin. 1992,8, 87. [林仲华, 王逢春,田中群. 物理化学学报, 1992, 8, 87.]doi: 10.3866/PKU.WHXB19920116
7. [7]
  (7) Zucchi, F.; Trabanelli, G.; Brunoro, G. Mater. Corros. 1993, 44,264.(7) Zucchi, F.; Trabanelli, G.; Brunoro, G. Mater. Corros. 1993, 44,264.
8. [8]
  (8) Wang, L. Corrosion Sci. 2001, 41, 1637.(8) Wang, L. Corrosion Sci. 2001, 41, 1637.
9. [9]
  (9) Li, X. H.; Deng, S. D.; Fu, H. Chin. J. Appl. Chem. 2012, 29,209. [李向红, 邓书端,付惠.应用化学, 2012, 29, 209.](9) Li, X. H.; Deng, S. D.; Fu, H. Chin. J. Appl. Chem. 2012, 29,209. [李向红, 邓书端,付惠.应用化学, 2012, 29, 209.]
10. [10]
  (10) Makhlouf, M. T.; El-Shahawy, A. S.; El-Shatory, S. A. Mater. Chem. Phys. 1996, 43, 153. doi: 10.1016/0254-0584(95)01611-W(10) Makhlouf, M. T.; El-Shahawy, A. S.; El-Shatory, S. A. Mater. Chem. Phys. 1996, 43, 153. doi: 10.1016/0254-0584(95)01611-W
11. [11]
  (11) Li, X. H.; Deng, S. D.; Fu, H. Corrosion Sci. 2009, 51, 1344.doi: 10.1016/j.corsci.2009.03.023(11) Li, X. H.; Deng, S. D.; Fu, H. Corrosion Sci. 2009, 51, 1344.doi: 10.1016/j.corsci.2009.03.023
12. [12]
  (12) Kokalj, A.; Peljhan, S.; Finšgar, M.; Milošev, I. J. Am. Chem. Soc. 2010, 132, 16657. doi: 10.1021/ja107704y(12) Kokalj, A.; Peljhan, S.; Finšgar, M.; Milošev, I. J. Am. Chem. Soc. 2010, 132, 16657. doi: 10.1021/ja107704y
13. [13]
  (13) Feng, L. J.; Yang, H. Y.; Wang, F. H. Electrochim. Acta 2011,58, 427. doi: 10.1016/j.electacta.2011.09.063(13) Feng, L. J.; Yang, H. Y.; Wang, F. H. Electrochim. Acta 2011,58, 427. doi: 10.1016/j.electacta.2011.09.063
14. [14]
  (14) El Adnani, Z.; Mcharfi, M.; Sfaira, M.; Benzakour, M.;Benjelloun, A. T.; Ebn Touhami, M. Corrosion Sci. 2013, 68,223. doi: 10.1016/j.corsci.2012.11.020(14) El Adnani, Z.; Mcharfi, M.; Sfaira, M.; Benzakour, M.;Benjelloun, A. T.; Ebn Touhami, M. Corrosion Sci. 2013, 68,223. doi: 10.1016/j.corsci.2012.11.020
15. [15]
  (15) Zhang, J.; Zhao, W. M.; Guo, W. Y.; Wang, Y.; Li, Z. P. Acta Phys. -Chim. Sin. 2008, 24, 1239. [张军,赵卫民,郭文跃,王勇,李中谱. 物理化学学报, 2008, 24, 1239.] doi: 10.3866/PKU.WHXB20080720(15) Zhang, J.; Zhao, W. M.; Guo, W. Y.; Wang, Y.; Li, Z. P. Acta Phys. -Chim. Sin. 2008, 24, 1239. [张军,赵卫民,郭文跃,王勇,李中谱. 物理化学学报, 2008, 24, 1239.] doi: 10.3866/PKU.WHXB20080720
16. [16]
  (16) Materials Studio 4.1; Accelrys Inc.: San Die , CA, 2006.(16) Materials Studio 4.1; Accelrys Inc.: San Die , CA, 2006.
17. [17]
  (17) Becke, A. D. J. Chem. Phys. 1988, 88, 2547. doi: 10.1063/1.454033(17) Becke, A. D. J. Chem. Phys. 1988, 88, 2547. doi: 10.1063/1.454033
18. [18]
  (18) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785(18) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
19. [19]
  (19) Klamt, A.; Schüürmann, G. J. Chem. Soc. Perkin. Trans. 1993,2, 799.(19) Klamt, A.; Schüürmann, G. J. Chem. Soc. Perkin. Trans. 1993,2, 799.
20. [20]
  (20) Cano, E.; Polo, J. L.; Iglesia, A. L.; Bastidas, J. M. Adsorption2004, 10, 219. doi: 10.1023/B:ADSO.0000046358.35572.4c(20) Cano, E.; Polo, J. L.; Iglesia, A. L.; Bastidas, J. M. Adsorption2004, 10, 219. doi: 10.1023/B:ADSO.0000046358.35572.4c
21. [21]
  (21) Zhang, F.; Tang, Y. M.; Cao, Z. Y.; Jing, W. H.; Wu, Z. L.; Chen,Y. Z. Corrosion Sci. 2012, 61, 1. doi: 10.1016/j.corsci.2012.03.045(21) Zhang, F.; Tang, Y. M.; Cao, Z. Y.; Jing, W. H.; Wu, Z. L.; Chen,Y. Z. Corrosion Sci. 2012, 61, 1. doi: 10.1016/j.corsci.2012.03.045
22. [22]
  (22) Behpour, M.; Ghoreishi, S. M.; Soltani, N.; Salavati-Niasari, M.Corrosion Sci. 2009, 51, 1073. doi: 10.1016/j.corsci.2009.02.011(22) Behpour, M.; Ghoreishi, S. M.; Soltani, N.; Salavati-Niasari, M.Corrosion Sci. 2009, 51, 1073. doi: 10.1016/j.corsci.2009.02.011
23. [23]
  (23) Bentiss, F.; Lebrini, M.; Lagrenée, M. Corrosion Sci. 2005, 47,2915. doi: 10.1016/j.corsci.2005.05.034(23) Bentiss, F.; Lebrini, M.; Lagrenée, M. Corrosion Sci. 2005, 47,2915. doi: 10.1016/j.corsci.2005.05.034
24. [24]
  (24) Vra?ar, L. M.; Dra??, D. M. Corrosion Sci. 2002, 44, 1669. doi: 10.1016/S0010-938X(01)00166-4(24) Vra?ar, L. M.; Dra??, D. M. Corrosion Sci. 2002, 44, 1669. doi: 10.1016/S0010-938X(01)00166-4
25. [25]
  (25) Solmaz, R.; Kardas, G.; Yazici, B.; Erbil, M. Colloids Surf. A2008, 312, 7. doi: 10.1016/j.colsurfa.2007.06.035(25) Solmaz, R.; Kardas, G.; Yazici, B.; Erbil, M. Colloids Surf. A2008, 312, 7. doi: 10.1016/j.colsurfa.2007.06.035
26. [26]
  (26) Moretti, G.; Guidi, F.; Grion, G. Corrosion Sci. 2004, 46, 387.doi: 10.1016/S0010-938X(03)00150-1(26) Moretti, G.; Guidi, F.; Grion, G. Corrosion Sci. 2004, 46, 387.doi: 10.1016/S0010-938X(03)00150-1
27. [27]
  (27) Li, X. H.; Deng, S. D.; Mu, G. N.; Fu, H.; Yang, F. Z. Corrosion Sci. 2008, 50, 420. doi: 10.1016/j.corsci.2007.08.014(27) Li, X. H.; Deng, S. D.; Mu, G. N.; Fu, H.; Yang, F. Z. Corrosion Sci. 2008, 50, 420. doi: 10.1016/j.corsci.2007.08.014
28. [28]
  (28) Granese, S. L.; Rosales, B. M.; Oviede, C.; Zerbino, J. O.Corrosion Sci. 1992, 33, 1439. doi: 10.1016/0010-938X(92)90182-3(28) Granese, S. L.; Rosales, B. M.; Oviede, C.; Zerbino, J. O.Corrosion Sci. 1992, 33, 1439. doi: 10.1016/0010-938X(92)90182-3
29. [29]
  (29) Mathur, P. B.; Vasudevan, T. Corrosion 1982, 38, 171. doi: 10.5006/1.3579270(29) Mathur, P. B.; Vasudevan, T. Corrosion 1982, 38, 171. doi: 10.5006/1.3579270
30. [30]
  (30) Cao, C. Corrosion Sci. 1996, 38, 2073. doi: 10.1016/S0010-938X(96)00034-0(30) Cao, C. Corrosion Sci. 1996, 38, 2073. doi: 10.1016/S0010-938X(96)00034-0
31. [31]
  (31) Behpour, M.; Ghoreishi, S. M.; Mohammadi, N.; Soltani, N.;Salavati-Niasari, M. Corrosion Sci. 2010, 52, 4046. doi: 10.1016/j.corsci.2010.08.020(31) Behpour, M.; Ghoreishi, S. M.; Mohammadi, N.; Soltani, N.;Salavati-Niasari, M. Corrosion Sci. 2010, 52, 4046. doi: 10.1016/j.corsci.2010.08.020
32. [32]
  (32) Labjar, N.; Lebrini, M.; Bentiss, F.; Chihib, N. E.; El Hajjaji, S.;Jama, C. Mater. Chem. Phys. 2010, 119, 330. doi: 10.1016/j.matchemphys.2009.09.006(32) Labjar, N.; Lebrini, M.; Bentiss, F.; Chihib, N. E.; El Hajjaji, S.;Jama, C. Mater. Chem. Phys. 2010, 119, 330. doi: 10.1016/j.matchemphys.2009.09.006
33. [33]
  (33) Lebrini, M.; Lagrenée, M.; Vezin, H.; Traisnel, M.; Bentiss, F.Corrosion Sci. 2007, 49, 2254. doi: 10.1016/j.corsci.2006.10.029(33) Lebrini, M.; Lagrenée, M.; Vezin, H.; Traisnel, M.; Bentiss, F.Corrosion Sci. 2007, 49, 2254. doi: 10.1016/j.corsci.2006.10.029
34. [34]
  (34) Priya, A. R. S.; Muralidharam, V. S.; Subramania, A. Corrosion2008, 64, 541. doi: 10.5006/1.3278490(34) Priya, A. R. S.; Muralidharam, V. S.; Subramania, A. Corrosion2008, 64, 541. doi: 10.5006/1.3278490
35. [35]
  (35) Osório, W. R.; Moutinho, D. J.; Peixoto, L. C.; Ferreira, I. L.;Garcia, A. Electrochim. Acta 2011, 56, 8412. doi: 10.1016/j.electacta.2011.07.028(35) Osório, W. R.; Moutinho, D. J.; Peixoto, L. C.; Ferreira, I. L.;Garcia, A. Electrochim. Acta 2011, 56, 8412. doi: 10.1016/j.electacta.2011.07.028
36. [36]
  (36) Lagrenée, M.; Mernari, B.; Bouanis, M.; Traisnel, M.; Bentiss,F. Corrosion Sci. 2002, 44, 573. doi: 10.1016/S0010-938X(01)00075-0(36) Lagrenée, M.; Mernari, B.; Bouanis, M.; Traisnel, M.; Bentiss,F. Corrosion Sci. 2002, 44, 573. doi: 10.1016/S0010-938X(01)00075-0
37. [37]
  (37) Li, D. Z.; Zhang, S. G.; Bian, H.; Zhang, L. C. Comput. Appl. Chem. 2009, 26, 324. [李大枝, 张士国,卞贺,张立超.计算机与应用化学, 2009, 26, 324. ](37) Li, D. Z.; Zhang, S. G.; Bian, H.; Zhang, L. C. Comput. Appl. Chem. 2009, 26, 324. [李大枝, 张士国,卞贺,张立超.计算机与应用化学, 2009, 26, 324. ]
38. [38]
  (38) Parr, R. G.; Yang, W. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036(38) Parr, R. G.; Yang, W. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036
39. [39]
  (39) Gómez, B.; Likhanova, N. V.; Aguilar, M. A. D.; Olivares, O.;Hallen, J. M.; Martínez-Magadán, J. M. J. Phys. Chem. A 2005,109, 8950. doi: 10.1021/jp052188k(39) Gómez, B.; Likhanova, N. V.; Aguilar, M. A. D.; Olivares, O.;Hallen, J. M.; Martínez-Magadán, J. M. J. Phys. Chem. A 2005,109, 8950. doi: 10.1021/jp052188k
40. [40]
  (40) Lashkari, M.; Arshadi, M. R. Chem. Phys. 2004, 299, 131. doi: 10.1016/j.chemphys.2003.12.019(40) Lashkari, M.; Arshadi, M. R. Chem. Phys. 2004, 299, 131. doi: 10.1016/j.chemphys.2003.12.019
41. [41]
  (41) Schweinsberg, D. P.; Ashworth, V. Corrosion Sci. 1988, 28, 539.doi: 10.1016/0010-938X(88)90022-4(41) Schweinsberg, D. P.; Ashworth, V. Corrosion Sci. 1988, 28, 539.doi: 10.1016/0010-938X(88)90022-4
42. [42]
  (42) Banerjee, G.; Malhotra, S. N. Corrosion 1992, 48, 10. doi: 10.5006/1.3315912(42) Banerjee, G.; Malhotra, S. N. Corrosion 1992, 48, 10. doi: 10.5006/1.3315912
43. [43]
  (43) Feng, Y.; Chen, S.; Zhang, H.; Li, P.;Wu, L.; Guo, W. Appl. Surf. Sci. 2006, 253, 2812. doi: 10.1016/j.apsusc.2006.05.061(43) Feng, Y.; Chen, S.; Zhang, H.; Li, P.;Wu, L.; Guo, W. Appl. Surf. Sci. 2006, 253, 2812. doi: 10.1016/j.apsusc.2006.05.061
44. [44]
  (44) Ju, H.; Kai, Z. P.; Li, Y. Corrosion Sci. 2008, 50, 865. doi: 10.1016/j.corsci.2007.10.009(44) Ju, H.; Kai, Z. P.; Li, Y. Corrosion Sci. 2008, 50, 865. doi: 10.1016/j.corsci.2007.10.009
45. [45]
  (45) Lukovits, I.; Kálmán, E.; Zucchi, F. Corrosion 2001, 57, 3. doi: 10.5006/1.3290328(45) Lukovits, I.; Kálmán, E.; Zucchi, F. Corrosion 2001, 57, 3. doi: 10.5006/1.3290328
46. [46]
  (46) Sastri, V. S.; Perumareddi, J. R. Corrosion 1997, 53, 617. doi: 10.5006/1.3290294(46) Sastri, V. S.; Perumareddi, J. R. Corrosion 1997, 53, 617. doi: 10.5006/1.3290294
47. [47]
  (47) Awad, M. K.; Mustafa, M. R.; Elnga, M. M. A. J. Mol. Struct. -Theochem 2010, 959, 66. doi: 10.1016/j.theochem.2010.08.008
  (47) Awad, M. K.; Mustafa, M. R.; Elnga, M. M. A. J. Mol. Struct. -Theochem 2010, 959, 66. doi: 10.1016/j.theochem.2010.08.008

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沈阳化工大学材料科学与工程学院沈阳 110142

嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

English

Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid Solution

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嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

English

Inhibition Effect of Pyrimidine Derivatives on the Corrosion of Steel in Hydrochloric Acid Solution

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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