Structure of water molecules from Raman measurements of cooling different concentrations of NaOH solutions

Accepted Manuscript Structure of water molecules from Raman measurements of cooling different concentrations of NaOH solutions

Fabing Li, Zhanlong Li, Shenghan Wang, Shuo Li, Zhiwei Men, Shunli Ouyang, Chenglin Sun PII: DOI: Reference:

S1386-1425(17)30342-6 doi: 10.1016/j.saa.2017.04.067 SAA 15120

To appear in:

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Received date: Revised date: Accepted date:

6 March 2017 13 April 2017 23 April 2017

Please cite this article as: Fabing Li, Zhanlong Li, Shenghan Wang, Shuo Li, Zhiwei Men, Shunli Ouyang, Chenglin Sun , Structure of water molecules from Raman measurements of cooling different concentrations of NaOH solutions. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Saa(2017), doi: 10.1016/j.saa.2017.04.067

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ACCEPTED MANUSCRIPT

Structure of water molecules from Raman measurements of cooling different concentration NaOH solutions

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Fabing Lia, Zhanlong Lia, Shenghan Wanga, Shuo Lia, Zhiwei Mena, Shunli Ouyangb*, Chenglin Suna*

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a Coherent Light and Atomic and Molecular Spectroscopy Laboratory, College of Physics, Jilin University, Changchun 130012, China b Key Laboratory of Integrated Exploitation of Bayan Obo Multi-Metal Resources, Inner Mongolia University of Science & Technology, Baotou 014010, China

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Abstract The Raman spectra of different concentration NaOH solutions

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have been successfully obtained at normal pressure by cooling. The results indicate that the icing point and the ice phase transition

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temperature of NaOH solutions decrease with increasing concentrations.

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Particularly, the different concentrations (2, 4, 6 or 8 and 12 M) take place the liquid- III- Ih, liquid- V- Ih, liquid- VI- XV and liquid- IX- VI

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phase transition, respectively. In addition, the three peaks of around 3524,

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3580 and 3624 cm-1 appear spectra of the NaOH solutions at low temperature.

Keywords Raman spectra; cooling; NaOH solutions; phase transition

*Corresponding author at: Coherent Light and Atomic and Molecular Spectroscopy Laboratory, College of Physics, Jilin University, 2699, Qianjing District, Changchun, China. Tel: +86 15043076988. Key Laboratory of Integrated Exploitation of Bayan Obo Multi-Metal Resources, Inner Mongolia University of Science & Technology, Baotou, China. Tel: 13847267569. E-mail address: [email protected] (C. L. Sun) and [email protected] (S. L. Ouyang).

ACCEPTED MANUSCRIPT 1. INTRODUCTION Water is one of the most important and basic materials in living systems. Despite its apparent molecular simplicity, it has long been considered as complex nature [1]. Aqueous solutions of sodium

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hydroxide are common in natural environments in biochemistry and

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geochemistry, which form electrolytes affecting phenomena such as

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membrane contaminant absorption and structure and function, moreover, they are extremely important in industrial contexts in nuclear waste

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processing and corrosion [2]. Furthermore, the critical temperatures for

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phase transition vary with the type and concentration of the solute [3]. Neutron scattering, empirical potential structure refinement (EPSR),

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infrared (IR) absorption, and Raman scattering are powerful tools used to

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research the phonon abundance transition, phonon relaxation dynamics in terms of bond stiffness, molecular fluctuation order and microscopic

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structure [4-8]. However, only little attention has been so far devoted to

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the NaOH solutions impact on the water icing and ice phase transition. Vibrational spectroscopy study on the water molecular structure and dynamics have been shown to be beneficially, both in the bulk and confined state, because the spectra are sensitive to local environment of the molecule [9-11]. In particular Raman spectra are one of the most commonly used techniques to study liquid and solid water, as it provides direct information on inter- and intra-molecular vibrational modes [12,13].

ACCEPTED MANUSCRIPT At the same time, it obtains the information of molecular vibration and rotation to understand the structure of water molecules and the interaction between water molecules and other materials [14,15]. Raman lines depend upon structural changes or phase transitions at the specific

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conditions (high or low temperatures, high pressure and interfaces) [16].

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In this paper, we present our work on Raman investigation on the icing

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and ice phase transition of normal pressure different concentration NaOH solutions. The results indicate that for the electric filed action strengthen

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with the increase of NaOH concentrations, the icing point and the ice

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phase transition temperature of NaOH solutions decrease with increasing concentration. Meanwhile, an appropriate intensity of the electric field

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makes bond disordering in water molecular arrangement, which resulting

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in the peak at about 3250 cm-1 disappears and one peak at about 3420 cm-1 appears in the 6 and 8 M liquid. More importantly, the interaction of

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hydrogen bond and electric field on different NaOH solutions leads to

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distinct phase transition. In addition, because the NaOH solutions can produce the OH- ions and hydrate-electron, the three peaks of about 3524, 3580 and 3624 cm-1 appear spectra of the NaOH solutions at low temperature. There results are significant to understand other the impurity species, such as acids, salts, etc, impact on the water icing and ice phase transition.

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2. EXPERIMENTAL The pure water and the liquid water of NaOH solutions have been deionized from triple distilled water and have been measured with a

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Raman micro spectrometer. The sample has been kept in the 10 mm of

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radius quartz disk. The water and NaOH solutions have been excited by

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an Argon laser at 5145 Å and an output power of 10 mW. The Raman spectra have been obtained using a Renishaw InVia Raman spectrometer.

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The spectra (shift range 2700-4000 cm-1) in backscattering configuration

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have been obtained by using a 50× long working distance objective lens located in the liquid water and the different concentration NaOH

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solutions. The spectra have been obtained at a scanning speed of

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10 cm-1/min. A 1200 lines/mm grating has used, which resulted in a spectral resolution of 4 cm-1. The spectra at low temperature have been

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obtained using a THMSG Linkam PE95 heating-freezing with 0.1 K

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accuracy at a temperature cool range from 273 to 83 K . Each temperature interval lasted for 10 min after collecting the spectrum.

3. RESULTS AND DISCUSSION Fig. 1 (a) shows the spectra of bulk water (blue) and ice Ih (hexagonal phase of ice,magenta).The peaks of bulk water at 3227 and 3387 cm-1 are attributed to symmetric and asymmetric O-H stretching vibrational mode,

ACCEPTED MANUSCRIPT respectively. Q. Du et al. believe that the peak intensity at 3227 cm-1 is an indication of bond ordering in the water molecular arrangement [17]. The Raman peaks of ice Ih locate at 3127, 3242, and 3338 cm−1. The region around 3338 cm−1 corresponds to local symmetric O-H stretching

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vibrational mode [18]. The maximum intensity of the region around 3127

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cm−1 is also observed, corresponding to local asymmetric O-H stretching

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vibrational mode [18-20]; the shoulder peak at around 3242 cm−1 is the overtone of bending modes. The Fermi resonance has been appeared

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between the bending overtone (around 3242 cm-1) and symmetric O-H

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stretching vibrational mode (around 3338 cm-1) in the stretching vibration region [19,20]. Fig. 1 (b) and Fig. 1a shows, respectively, the spectra of 2

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M NaOH solutions icing and the Raman shift vs temperature. Fig. 1a (a)

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illustrates that the Raman shift occurs mutation and meanwhile the Raman spectra produce the new Raman peak at 257 K. These results

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demonstrate that the structure of pure water take place change (the icing

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and the ice phase transition). By comparing Fig. 1a (a) with Fig. 1a (b), we find that the icing point of 2 M NaOH solutions is lower than that of pure water.

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a -1 -1 3127 cm 3387 cm -1 3227 cm

b

268K 258K 257K

258K 254K 253K 243K 233K

-1

3121 cm -1

-1

Raman intensity/a.u

3242 cm -1 3338 cm

3145 cm -1 3287 cm

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-1

-1

3330 cm

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3232 cm

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2750 3000 3250 3500 3750 4000 3000 3250 3500 3750 4000 Raman shift /cm

-1

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Fig. 1 Raman spectra of the icing. (a), pure water; (b), 2 M NaOH

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asymmetric OH stretch overtone of bending modes asymmetric Oh stretch

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3450 3400 a 3350 3300 3250 3200 3150 3100 3050 3400 b 3350 3300 3250 3200 3150 3100 3050 280 260

asymmetric OH stretch overtone of bending modes asymmetric Oh stretch

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Raman shift /cm

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solution.

240

220

200

180

160

140

120

100

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Temperature /k

Fig. 1a Raman shift vs temperature. (a), pure water; (b), 2 M NaOH solution.

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a

b

-1

3100 cm

243K 233K 223K 183K 173K

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3144 cm

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3310 cm

233K 228K 183K 153K 143K

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-1

3440 cm

3110 cm

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3290 cm

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3340 cm

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3245 cm

c

d

233K 223K 193K 153K 133K

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3113 cm

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-1

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3075 cm

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3310 cm

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3454 cm

233K 223K 203K 113K 103K

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3290 cm -1 3433 cm

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3238 cm 3440 cm -1 3393 cm

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Raman intensity/a.u

-1

3092 cm

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3092 cm -1 3282 cm 3355 cm-1

-1

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3100 cm

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3459 cm

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3319 cm

2750

3000

3250

3500

3750

4000 2750

3000

3250

3500

3750

4000

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-1 Raman shift /cm

3450

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Fig. 2 Raman spectra of the icing. (a), 4 M; (b), 6 M; (c), 8 M; (d), 12 M.

a

3250 3200

3100

3500 3450

3400

260

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220

c

200

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3350 3300 3250 3200 3150 3100 120

100

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3050 280

240

220

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asymmetric OH stretch asymmetric Oh stretch bifurcated hydrogen bond the non-in-phase OH stretch

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120

100

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asymmetric OH stretch asymmetric Oh stretch bifurcated hydrogen bond

3500 3450 3400

3350

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3300

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3250

3250

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3150

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3100 3050 280

260

3550

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3400

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Raman shift /cm

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3150

3550

3450

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3300

asymmetric OH stretch asymmetric Oh stretch bifurcated hydrogen bond the non-in-phase OH stretch

b

3500

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3350

3050 280

3550

asymmetric OH stretch overtone of bending modes asymmetric Oh stretch

3400

3100 260

240

220

200

180

160

140

120

100

80

3050 280

260

240

220

200

180

160

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Temperature /k

Fig. 2a Raman shift vs temperature. (a), 4 M; (b), 6 M; (c), 8 M; (d), 12 M.

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2800

3000

3200

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R am an intensity /a.u

0M 2M 4M 6M 8M 12M

3400

3600

3800

4000

-1

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Raman shift /cm

Fig. 3 Raman spectra of the different concentration NaOH solutions at

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273 K.

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Fig. 2 presents the Raman spectra of different concentration NaOH solutions icing. The Raman shift vs temperature of NaOH solutions is Fig.

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2a. Comparing Fig. 1a (b) with Fig. 2a, we observe the temperature

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change of Raman shift occurs mutation and meanwhile spectra produce the new Raman peak, demonstrating that the icing point and the ice phase transition temperature of NaOH solutions decrease with increasing concentrations. The icing point of these concentration NaOH solutions (2, 4, 6, 8 and 12 M) is about 253, 233, 228, 223 and 223 K, respectively. At the same time, the ice phase transition temperature of NaOH solutions with different concentrations is respectively about 233, 173, 143, 133 and

ACCEPTED MANUSCRIPT 103 K. In addition, Raman spectra of the different concentration NaOH solutions at 273 K is Fig. 3, showing the peaks of O-H stretching vibrational mode undergo a blue shift (from 3250 to 3420 cm-1) in the 6 and 8 M liquid, which effect the same as heating [21]. The assignment of

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the peak at 3420 cm-1 is still debate. J. Scherer et al. consider it to be the

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symmetric O-H stretching vibrational mode of asymmetrically bonded

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water molecules [22], where the two H of the water molecules are bonded to the neighboring water molecules by strong and weak hydrogen bond,

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respectively. Others consider it to molecules with bifurcated hydrogen

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bond [23]. In any case this peak strength is an indication of bond disordering in water molecular arrangement [17].

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By comparing the Raman shift and relative intensities of all

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concentration NaOH solutions icing (Fig. 1(b) and Fig. 2) with that of ice [24-26], we find that, in the low concentration (2 M), the two peaks 3145

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and 3287 cm-1 at 253 K correspond to the peaks 3159 and 3281 cm-1 of

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ice III (tetragonal phase), the three peaks (3121, 3232 and 3330 cm-1) at 233 K is similar to that of ice Ih (Fig. 1 (a), hexagonal phase). In the 4 M, the spectra of 233 K appear two peaks at about 3144 and 3310 cm-1, which respectively correspond to the 3181 and 3312 cm-1 of ice V (monoclinic phase),when the temperature drops to 173 K, the three peaks of 3100, 3245 and 3340 cm-1 are alike to that of ice Ih. In the medium concentration water (6 and 8 M), at 228 and 223 K, the peaks at about

ACCEPTED MANUSCRIPT 3110, 3290 and 3440cm-1 is similar to that of ice VI (three-phase), respectively; The spectra of ice phase transition (143 and 133 K) appear four peaks at about 3092, 3238, 3393 and 3440 cm-1, corresponding to that of ice XV (hydrogen-ordered phase). Finally, the Raman spectra of

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icing (223 K) appear the two peaks at about 3100 and 3319 cm -1 in the

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high concentration NaOH solutions (12 M), which are the peaks of ice IX

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(tetragonal phase), in addition, the three peaks at about 3075, 3310 and 3454 cm-1 appear at 103 K, meaning the ice phase transition is from ice

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IX to ice VI.

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Consequently, we can obtain Table 1. The icing point /K

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Concentration /M

Phase transition

temperature /K

257

None

Liquid- Ih

253

233

Liquid- III- Ih

233

173

Liquid- V- Ih

228

143

Liquid- VI- XV

8

223

133

Liquid- VI- XV

12

223

103

Liquid- IX-VI

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0

The ice phase transition

4

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6

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2

Table 1 The icing point, the ice phase transition temperature and phases transition of different NaOH solutions.

The NaOH solutions form the hydration shell of the OH- ion, the

ACCEPTED MANUSCRIPT coordination water molecule numbers of the OH- ions solvation shell are close to five at the lowest NaOH concentrations and decreases to about three at the highest NaOH concentrations [4,5]. There are about four or three water molecules strongly hydrogen bonding to oxygen of the OH-

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ions through their hydrogen, another water molecule is weakly hydrogen

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bonding to the hydrogen of the OH- ions. Moreover, water molecules

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interact through hydrogen bonds. The hydrogen bond effect gradually increase with the decrease of temperature, resulting in the shortening and

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stiffening O...H nonbond and meanwhile the lengthening and softening

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H-O bond through O-O coulomb repulsion [27]. Researches show that the first solvation shell of the sodium ion contains on average 5.2 water

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molecules by first-principles simulation and the Na+ does not effect on

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the water molecules orientation outside the first hydration shell [28]. Interestingly, the NaOH solutions create an ionic field (electric field),

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which leads to the O...H nonbond lengthening and softening, and

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meanwhile the H-O bond contraction and stiffening through O-O repulsion, we find that the ionic field mechanical compression does the opposite effect the O...H-O bond relaxation [29]. The effect of ionic field strengthen with the increase of NaOH concentrations, indicating that the cooling does the opposite to solute electrification upon the O...H-O bond relaxation, which requires more energy for the same sequence of phase transitions. Therefore, the icing point and the ice phase transition

ACCEPTED MANUSCRIPT temperature of NaOH solutions decrease with increasing concentration. Meanwhile, an appropriate intensity of the electric field makes bond disordering in water molecular arrangement, resulting in the O-H stretching vibrational mode Raman shift from 3250 to 3420 cm-1 at 6 and

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8 M liquid NaOH solutions. In addition, the interaction between hydrogen

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bond and electric field lead to the formation of distinct ice phases during

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icing in the different concentration NaOH solutions. The different concentrations at 2, 4, 6 (8) and 12 M correspond to the phases of ice III,

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V, VI and IX, respectively. At the same time, with the decrease of

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temperature, hydrogen bonding plays a major role, which leads to the IIIIh and V- Ih phase transition in the 2 and 4 M solutions. The strength of

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hydrogen bonding and electric field action is equally matched in the

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medium concentration (6 and 8 M) at cold, so the ice phase transition undergoes from VI to XV. In the 12 M solutions, however, for the electric

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field is very strong, the ice IX- VI phase transition occurs at low

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temperature. The temperature, pressure and other conditions (such as the order of phase transition) required for these ice phases formation are known from the ice phase diagrams and previously researches [30-34]. A. Botti et al. find that the interaction between the solute and the tetrahedral network of hydrogen bond water molecules in a manner is similar to the application of high pressure to pure water [4]. Fig. 4 shows the relationship between equivalent pressure on different NaOH solutions and

ACCEPTED MANUSCRIPT molarity, which indicates that the pressure amplify with concentration increase. This result shows that the different concentration NaOH solutions produce the required pressure to form the corresponding phases. The temperature and other conditions required also can be achieved.

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Therefore, the different NaOH solutions take place distinct phase

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transition.

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900 800

820

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670

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600 550

500

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400 300 200

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equivalent pressure /MPa

750

700

200

2

3

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1

4

5

6

7

8 1

molarity /mol L

9

10

11

12

13

-1

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Fig. 4 Equivalent pressure for the different NaOH solutions vs molarity calculated according to Ref 4.

In addition, Fig. 5 shows that Raman spectra of the 2 M NaOH solutions at low temperature, we find that the spectra appear three peaks locate at about 3524, 3580 and 3624 cm-1. Generally, the two peaks at 3524 and 3624 cm-1 are attributed to water molecules whose hydrogen

ACCEPTED MANUSCRIPT bond has been broken in part or in all. The 3524 cm-1 is belong to hydrogen bonded O-H stretching vibrational mode of water molecules in which one proton is not involved in linear hydrogen bonds [35]. The shoulder peak at about 3624 cm-1 is assignment to free OH vibrational

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mode. These results are caused by the OH- ion of NaOH solutions, which

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leads to the fully hydrogen bonded water arrangements reduction and the

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partly hydrogen bonded and free OH addition. Specifically, due to the NaOH solutions can produce hydrate-electron, the peak at 3580 cm-1

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corresponds to e−aqs (form the hydrate electron) resonance enhancement

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O-H stretching vibrational mode of the water hexamer [36]. Raman spectra of the other concentration NaOH solutions at low temperature

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present Fig. 6, which manifests that other concentrations also appear

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these three peaks, while is not obvious.

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Raman intensity/a.u

213K 183K

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-1

3524 cm

-1

3250

3500

3750

4000

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3000

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3580 cm -1 3624 cm

Raman shift /cm

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Fig. 5 Raman spectra of the 2 M NaOH solutions at low temperature.

b

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a

183K 143K

193K 183K

-1

3530 cm -1 3580 cm -1 3600 cm

-1

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d

c

2750

143K 103K

173K 133K

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Raman intensity/a.u

3516 cm -1 3560 cm -1 3602 cm

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3510 cm

-1

3532 cm -1 3580 cm -1 3614 cm

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3580 cm

-1

3614 cm

3000

3250

3500

3750

4000

2800

3000

3200

3400

3600

3800

4000

-1

Raman shift /cm

Fig. 6 Raman spectra of the different NaOH solutions at low temperature. (a), 4 M; (b), 6 M; (c), 8 M; (d), 12 M.

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4. CONCLUSIONS The Raman spectroscopy has been used to investigate the icing point

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and the ice phase transition of cooling NaOH solutions with different

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concentrations at normal pressure. The results indicate that because the

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effect of ionic field strengthen with the increase of NaOH concentrations, the icing point and the ice phase transition temperature of the NaOH

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solutions decrease with increasing concentrations. Meanwhile, an

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appropriate intensity of the electric field makes bond disordering in water molecular arrangement, which resulting that the 6 or 8 M NaOH at liquid

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has the same action as heating on the Raman shift from 3250 to 3420 cm-1.

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The interaction of hydrogen and electric field on different NaOH solutions leads to distinct phase transition, and Raman spectra clarifies

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phase transition the following:

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(1) In the 2 M, the liquid- III- Ih phase transition take place at 253 and 233 K.

(2) In the 4 M, the liquid- V- Ih phase transition appear at 233 and 173 K. (3) In the 6 and 8 M, the liquid- VI- XV phase transition occur in 228 and 143 K. (4) In the 12 M, taking place the liquid- IX- VI phase transition at 223

ACCEPTED MANUSCRIPT and 103 K. In particular, for the NaOH solutions can produce the OH- ions and hydrate-electron, the three peaks of around 3524, 3580 and 3624 cm-1 appear spectra of the NaOH solutions at low temperature. These results

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are significant to understand the icing and ice phase transition with other

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impurity species such as acids, salts, etc.

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Fundings: This work was supported by National Natural Science Foundation of China (NSFC)

(20140101174JC, 20140204051GX).

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ACCEPTED MANUSCRIPT interpretation of the Raman spectra of hydrogen‐ordered ice XV, J. Raman. Spectrosc. 44 (2013) 290-298. [28]J. A. White, E. Schwegler, G. Galli, F. Gygi, The solvation of Na+ in water: First-principles simulations, J. Chem. Phys. 113 (2000)

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4468-4473.

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Q. Sun, B. Zou, Compression icing of room-temperature NaX solutions (X= F, Cl, Br, I), Phys. Chem. Chem. Phys. 18 (2016)

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14046-14054.

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[30]W. F. Kuhs, T. C. Hansen, Time-resolved neutron diffraction studies with emphasis on water ices and gas hydrates, Rev. Mineral.

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Geochem. 63 (2006) 171.

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[31]C. G. Salzmann, P. G. Radaelli, E. Mayer, J. L. Finney, Ice XV: A new thermodynamically stable phase of ice, Phys. Rev. Lett. 103

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(2009) 105701.

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[32]J. D. Londono, W. F. Kuhs, J. L. Finney, Neutron diffraction studies of ices III and IX on under-pressure and recovered samples, J. Chem. phys. 98 (1993) 4878-4888. [33]B. Kamb, A. Prakash, C. Knobler. Structure of ice V, Acta. Crystallogr. 22 (1967) 706-715. [34]W. F. Kuhs, J. L. Finney, C. Vettier, D. V. Bliss, Structure and hydrogen ordering in ices VI, VII, and VIII by neutron powder

ACCEPTED MANUSCRIPT diffraction, J. Chem. Phys. 81 (1984) 3612-3623. [35]V. Crupi, S. Interdonato, F. Longo, D. Majolino, P. Migliardo, V. Venuti, A new insight on the hydrogen bonding structures of nanoconfined water: a Raman study, J. Raman. Spectrosc. 39 (2008)

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244-249.

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[36]Z. W. Men, W. H. Fang, Z. W. Li, C. L. Sun, Z. L. Li, X. J. Wang,

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Hydrated-electron resonance enhancement O-H stretching vibration of water hexamer at air-water interface. Opt. Lett. 40 (2015)

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1434-1437.

ACCEPTED MANUSCRIPT Graphical abstract

a -1 -1 3127 cm 3387 cm -1 3227 cm

268K 258K 257K

b

258K 254K 253K 243K 233K

-1

3121 cm -1

-1

3145 cm -1 3287 cm

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Raman intensity/a.u

3242 cm -1 3338 cm

-1

-1

3330 cm

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3232 cm

2750 3000 3250 3500 3750 4000 3000 3250 3500 3750 4000 -1

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Raman shift /cm

a

solution.

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Fig. 1 Raman spectra of the icing. (a), pure water; (b), 2 M NaOH

b

-1

3100 cm

243K 233K 223K 183K 173K

-1

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3144 cm

Raman intensity/a.u

-1

-1

3440 cm

3110 cm

-1

3290 cm

-1

3340 cm

-1

3245 cm

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-1

3310 cm

233K 228K 183K 153K 143K

-1

3092 cm

c

233K 223K 193K 153K 133K

-1

3113 cm

-1

3290 cm -1 3433 cm

-1

-1

3238 cm 3440 cm -1 3393 cm

d 233K 223K 203K 113K 103K

-1

3075 cm

-1

3310 cm

-1

3454 cm

-1

3092 cm -1 3282 cm 3355 cm-1

-1

3100 cm -1

3459 cm

-1

3319 cm

2750

3000

3250

3500

3750

4000 2750

3000

3250

3500

3750

4000

-1 Raman shift /cm

Fig. 2 Raman spectra of the icing. (a), 4 M; (b), 6 M; (c), 8 M; (d), 12 M.

ACCEPTED MANUSCRIPT Highlights  We find that the icing point and the ice phase transition temperature of NaOH solutions decrease when the concentration increases. In addition, at liquid of the 6 or 8 M NaOH solutions, the peaks have the

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same action as heating on the Raman shift from 3250 to 3420 cm-1.

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 Due to the interaction of hydrogen and electric field on different

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NaOH solutions, the different concentrations (2, 4, 6 or 8 and 12 M) take place the liquid- III- Ih, liquid- V- Ih, liquid- VI- XV and liquid-

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IX- VI phase transition, respectively.

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 Because the NaOH solutions can produce the OH- ions and hydrate-electron, at low temperature, the three peaks at around 3524,

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3580 and 3624 cm-1 appear spectra of the NaOH solutions.