Raman Spectroscopic Investigation on the Effect of Hydrogen Bond on Molecular Structure in Ternary Aqueous Solution†

doi:10.7503/cjcu20170445

Abstract

Abstract:

The effect of hydrogen bond on the molecular structure in water-acetonitrile-dimethyl sulfoxide ternary system was investigated by Raman spectroscopy. The molecular interactions in water-acetonitrile-dimethyl sulfoxide ternary system, with different molar ratios were investigated by Raman spectroscopy. The results show that the electron cloud of the C≡≡N bond get closer to carbon atom, while the electron cloud of the S＝O bond get closer to sulfur atom in ternary mixture. In addition, there exists an obviously competitive relationship between acetonitrile and DMSO when they form hydrogen bond with water in this ternary system, and there exists the situation in which acetonitrile molecule and DMSO molecule share one water molecule to form the compounds. With increasing the proportion of water, this situation gradually disappears. The research provides experimental basis for enriching the hydrogen bonding theory in ternary aqueous solution system.

Key words: Water-acetonitrile-dimethyl sulfoxide ternary system, Aqueous solution, Hydrogen bond, Raman spectroscopy

CLC Number:

O641

TrendMD:

OUYANG Shunli, ZHANG Mingzhe, ZHANG Yongzhao, HU Qingcheng, WEI Haiyan, WU Nannan, HUANG Baokun. Raman Spectroscopic Investigation on the Effect of Hydrogen Bond on Molecular Structure in Ternary Aqueous Solution^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 758.

Figures/Tables 11

Fig.1 Structure of Raman spectrometer

Table 1 Molar contents of each sample

Sample	n(Water):n(acetonitrile): n(DMSO)	Sample	n(Water):n(acetonitrile): n(DMSO)	Sample	n(Water):n(acetonitrile): n(DMSO)
a	1:0:0	f	0:1:1	k	1.5:1:1
b	0:0:1	g	0.5:1:1	l	1.6:1 :1
c	0:1:0	h	1:1:1	m	1.8:1:1
d	1:1:0	i	1.2:1:1	n	2.0:1:1
e	1:0:1	j	1.4:1:1	o	2.5:1:1

Fig.2 Raman peaks of C≡≡N bond in neat acetonitrile(sample c) and acetonitrile-H2O solution(sample d)

Fig.3 Raman peaks of C≡≡N bond in acetonitrile-DMSO solution(sample f) and neat acetonitrile(sample c)

Fig.4 Raman peaks of S=O bond in neat DMSO(sample b) and DMSO-H2O solution(sample e)

Fig.5 Raman peaks of S=O bond in neat DMSO(sample b) and acetonitrile-DMSO solution(sample f)

Fig.6 Raman peaks of C≡≡N bond in ternary solution(molar ratio 1:1:1, sample h) and neat acetonitrile(sample c)

Fig.7 Ternary complex composed of water, acetonitrile and DMSO

Fig.8 Raman peak of O-H bond in pure water(sample a), DMSO-H2O solution(sample e, 1:1), acetonitrile-H2O solution(sample d, 1:1) and ternary solution(sample h, 1:1:1)

Fig.9 Raman peak of S=O bond in neat DMSO(sample b) and ternary solution(sample h, 1:1:1)

Fig.10 Raman peaks of S=O bond(A) and C≡≡N bond(B) in ternary solutions(X:1:1) with water content(X) from 0.5 to 2.5 and changes of vibration peaks of S=O and C≡≡N bonds with water concentration(C)For samples g-o, X=0.5, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.5, respectively.

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