Yong Zhou,Danping Wu,Yinyan Gong,Zengsheng Ma,Yongli Huang,Xi Zhang,Chang Q Sun
We show phonon spectrometrically that the unprecedented H 2 Ö: ↔ :Ö:H – compression resolves the performance of the base solution networks with “:” being the electron lone pair of oxygen. At hydration, LiOH, NaOH, KOH molecules dissolve each into a :Ö:H – hydroxide and cations of Li + , Na + , and K + , respectively. The cations serve as charge centers to polarize the neighboring water molecules and raise the solution skin stress (or surface tension). The :Ö:H – tetrahedron adds, however, three lone pairs and one bonded H + proton to the solution matrix, turning the initially 2N lone pairs into 2N + 3 and the 2N bonded H + into 2N + 1 with an additional O 2– anion. This hydration process breaks the conservation of the 2N lone pairs and protons with two extra lone pairs that only can form a H 2 Ö: ↔ :Ö:H – super hydrogen bond (super-HB) with strong repulsivity. In addition to the H O bond of the :Ö:H – featured at 3610 cm − 1 , the internal H 2 Ö: ↔ :Ö:H – compression has an identical effect of mechanical compression, shortening the O:H nonbonds and stiffening their phonons from below 200 cm − 1 to the above. Meanwhile, compression lengthens the network H O bonds and softens their phonons from above 3150 cm − 1 to below. The network H O bonds elongation decreases their energy from ~ 4.0 to ~ 2.7 eV at hydration, which heats the solution as one often observes. The H 2 Ö: ↔ :Ö:H – super-HB compressor and the alkali cation polarizor form the keys to the base hydration networks and the properties.
Xi Zhang,Yan Xu,Yong Zhou,Yinyan Gong,Yongli Huang,Chang Q Sun
An incorporation of the hydrogen bond (O:H O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent H O bond phonon from 3200 to 3480 cm −1 in the hydration shells. The HO − in alkaline solution, however, shares not only the same H O phonon redshift of compressed water from 3200 to < 3100 cm −1 but also the dangling bonds of H 2 O surface featured at 3610 cm −1 . Salt and alkaline solvation enhances the solution surface stress by K + and Cl − ionic polarization. The excessive H + proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:H O bonds of the solvent matrix is featured by: f H = 0 and f x ∝ 1-exp(-C/C 0 ) (x = HO − , K + and Cl − ) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.
Yong Zhou,Yinyan Gong,Yongli Huang,Zengsheng Ma,Xi Zhang,Chang Q. Sun
Solvation of acid, base, and salt is ubiquitously important to all subject areas in chemistry , health care and life science. However, fine resolution of the solvation dynamics, solute-solvent molecular interactions , and solute capability of transforming the hydrogen bond (O:H O, or HB) and surface stress remain great challenge. Incorporating the notion of O:H O bond cooperativity with a strategy of differential phonon spectroscopy (DPS) has enabled resolution on the fraction and stiffness of the solvent HB from the mode of water to the hydration shells upon NaOH, NaI and HI solvation. Results show that Na + and I + ionic polarization shortens the H O bond and stiffens its phonon from 3200 to 3500 cm − 1 in the hydration shells. The H + in the HI solution forms a H ↔ H anti-HB that disrupts the solution network and surface stress. The excessive electron lone pairs of OH – form the O : ⇔ : O super-HB that compresses the network, sharing the same effect of mechanical compression shifting the H O phonon from above 3100 cm − 1 to its below; the solute H O bond performs the same to the H O dangling bond at surface featured at 3610 cm − 1 . The fraction coefficients or phonon abundance transition, f H = 0, f HO ∝ C, and f x ∝ 1-exp(− C/C 0 ) (x = Na + and I − and C the solute concentration) towards saturation, feature the solute capability of HB transformation. Practice not only confirms the essentiality of the H ↔ H anti-HB point fragilization, the O : ⇔ : O super-HB point compression, and the ionic polarization to the performance of the respective HI, NaOH, and NaI solutions, but also demonstrate the power of the DPS that enables fine-resolution of solvation dynamics and solute capabilities.
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