The critical temperatures of isomeric pentanols and heptanols

The critical temperatures of seven isomeric alcohols have been measured using the modified sealed tube method of Mogollon. The ampoule used in the Mogollon method was modified to allow easier handling and reproducible results to be obtained. The addition of an Apple IIe microcomputer to the apparatus made possible the recording of the temperature history of the fluid and the monitoring of successive meniscus disappearances and appearances with time. The critical temperatures were obtained by averaging the temperatures of meniscus disappearance and reappearance. The fill densities of the ampoules were approximately equal to the critical densities.     

Evaporation rate in containers used for storing radioactive tracer solutions

In radiochemical analysis, the storage of a tracer solution is an important issue to bear in mind. The evaporation of the tracer solution depends on the type of container used for storing. In this paper the evaporation rate in four kinds of containers, i.e., flame-sealed glass ampoule, sealed glass flask, flame-sealed polyethylene ampoule and screw glass vial was studied. It is concluded that the evaporation rate depends on the system of closing.     

Vapour pressure of DSC calibration substances

For a large number of DSC calibration substances the vapour pressure at room temperature or at transition temperature (whichever is the highest) is given. It is important to know the vapour pressure of substances, because a DSC measurement on a substance with a high vapour pressure requires encapsulation of the substance in a hermetically sealed crucible to prevent evaporation. Because the calibration procedure must be performed using the same type of sample pan as will be used during the actual measurements, the presented information allows one to decide which calibration substances and/or what type of sample pan should be used for calibration.This revised version was published online in November 2005 with corrections to the Cover Date.     

Prediction of macroscopic properties of protic ionic liquids by ab initio calculations

We have systematically investigated combinations of anions and cations in a number of protic ionic liquids based on alkylamines and used ab initio methods to gain insight into the parameters determining their liquid range and their conductivity. A simple, almost linear, relation of the experimentally determined melting temperature with the calculated volume of the anion forming the ionic liquid is found, whereas the dependence of the melting temperature with increasing cation volume goes through a minimum for relatively short side chain length. On the basis of the present results, we propose a strategy to predict the nature of protic ionic liquids in terms of low vapor pressure and conductivity. Comparisons with previously reported strategies for prediction of melting temperatures for aprotic ionic liquids are also made.     

Simultaneous spreading and evaporation: Recent developments

The recent progress in theoretical and experimental studies of simultaneous spreading and evaporation of liquid droplets on solid substrates is discussed for pure liquids including nanodroplets, nanosuspensions of inorganic particles (nanofluids) and surfactant solutions. Evaporation of both complete wetting and partial wetting liquids into a nonsaturated vapour atmosphere are considered. However, the main attention is paid to the case of partial wetting when the hysteresis of static contact angle takes place. In the case of complete wetting the spreading/evaporation process proceeds in two stages. A theory was suggested for this case and a good agreement with available experimental data was achieved. In the case of partial wetting the spreading/evaporation of a sessile droplet of pure liquid goes through four subsequent stages: (i) the initial stage, spreading, is relatively short (1–2 min) and therefore evaporation can be neglected during this stage; during the initial stage the contact angle reaches the value of advancing contact angle and the radius of the droplet base reaches its maximum value, (ii) the first stage of evaporation is characterised by the constant value of the radius of the droplet base; the value of the contact angle during the first stage decreases from static advancing to static receding contact angle; (iii) during the second stage of evaporation the contact angle remains constant and equal to its receding value, while the radius of the droplet base decreases; and (iv) at the third stage of evaporation both the contact angle and the radius of the droplet base decrease until the drop completely disappears. It has been shown theoretically and confirmed experimentally that during the first and second stages of evaporation the volume of droplet to power 2/3 decreases linearly with time. The universal dependence of the contact angle during the first stage and of the radius of the droplet base during the second stage on the reduced time has been derived theoretically and confirmed experimentally. The theory developed for pure liquids is applicable also to nanofluids, where a good agreement with the available experimental data has been found. However, in the case of evaporation of surfactant solutions the process deviates from the theoretical predictions for pure liquids at concentration below critical wetting concentration and is in agreement with the theoretical predictions at concentrations above it.     

Free release static coating of glass capillary columns; Static coating at elevated pressure — Theoretical considerations and practice

Summary Static coating of glass capillary columns has hitherto solely been carried out by evaporation of the stationary phase solvents under vacuum conditions. However, since a solvent vapour pressure higher than the external pressure is the only requirement for the vapour to flow out of the column, evacuation should not be necessary. Several important factors in the static coating procedure, such as mass (solvent vapour) — and heat transfer, heat of vaporisation of the solvent and viscosity of the stationary phase solution at elevated temperature and outlet pressure are discussed, principally to rationalise an improved static coating procedure. The alternative, so-called free-release static coating procedure, was evaluated practically by coating several columns with OV-101 and SE-30. Coating speed was found to be rapid and relatively constant whereas coating efficiency was between 80 and 100%.     

Correlation between thermodynamic and kinetic fragilities in nonpolymeric glass-forming liquids

A phenomenological relationship between reduced excess heat capacity of supercooled liquid DeltaC(p)(exc)(T(g))DeltaS(m) at the glass transition temperature T(g), fragility index m, and reduced glass transition temperature T(rg)=T(g)T(m), where T(m) is the melting (liquidus) temperature, was derived for fragile nonpolymeric glass-forming liquids under the assumptions that the fragile behavior of these liquids is described by the Vogel-Fulcher-Tammann (VFT) equation; the excess heat capacity of liquid is inversely proportional to the absolute temperature and the VFT temperature T(0) is equal to the Kauzmann temperature T(K). It was found that DeltaC(p)(exc)(T(g))DeltaS(m) is a composite function of m and T(rg), which indicates that the empirical correlation DeltaC(p)(exc)(T(g))DeltaS(m)=0.025m recently identified by Wang et al. [J. Chem Phys. 125, 074505 (2006)] is probably valid only for liquids which have nearly the same values of T(rg).     

Disjoining pressure and capillarity in the constrained vapor bubble heat transfer system

Using the disjoining pressure concept in a seminal paper, Derjaguin, Nerpin and Churaev demonstrated that isothermal liquid flow in a very thin film on the walls of a capillary tube enhances the rate of evaporation of moisture by several times. The objective of this review is to present the evolution of the use of Churaev's seminal research in the development of the Constrained Vapor Bubble (CVB) heat transfer system. In this non-isothermal "wickless heat pipe", liquid and vapor flow results from gradients in the intermolecular force field, which depend on the disjoining pressure, capillarity and temperature. A Kelvin-Clapeyron model allowed the use of the disjoining pressure to be expanded to describe non-isothermal heat, mass and momentum transport processes. The intermolecular force field described by the convenient disjoining pressure model is the boundary condition for "suction" and stability at the leading edge of the evaporating curved flow field. As demonstrated by the non-isothermal results, applications that depend on the characteristics of the evaporating meniscus are legion.     

The vapour pressure of naphthalene

Measurements of the vapour pressure of naphthalene over the temperature range 263 to 343 K are reported. These have been correlated with data from the literature, and an equation is given from which recommended values are calculated for the vapour pressure of solid naphthalene from 230 K to the triple point. An equation is given also for the vapour pressure of liquid naphthalene from the triple point to the critical point. The enthalpy of melting obtained by differentiating these two equations is in good agreement with a measured value.     

Discontinuous liquid rise in capillaries with varying cross-sections

We consider theoretically liquid rise against gravity in capillaries with height-dependent cross-sections. For a conical capillary made from a hydrophobic surface and dipped in a liquid reservoir, the equilibrium liquid height depends on the cone-opening angle alpha, the Young-Dupré contact angle theta, the cone radius at the reservoir's level R(0), and the capillary length kappa(-)(1). As alpha is increased from zero, the meniscus' position changes continuously until, when alpha attains a critical value, the meniscus jumps to the bottom of the capillary. For hydrophilic surfaces the meniscus jumps to the top. The same liquid height discontinuity can be achieved with electrowetting with no mechanical motion. Essentially the same behavior is found for two tilted surfaces. We further consider capillaries with periodic radius modulations and find that there are few competing minima for the meniscus location. A transition from one to another can be performed by the use of electrowetting. Finite pressure difference between the two sides of the liquids can be incorporated as well, resulting in complicated phase-diagrams in the alpha-theta plane. The phenomenon discussed here may find uses in microfluidic applications requiring the transport small amounts of water "quanta" (volume < 1 nL) in a regular fashion.     

Thermogravimetric analysis for boiling points and vapour pressure

A TGA instrument has been adapted for rapid measurement of boiling points and vapour pressure at temperatures from ambient up to 400°C and pressures from ambient down to 20 mm Hg. Samples were contained in sealed holders having a laser-drilled aperture. Several organic liquids in the 100 to 300 gMW range showed good agreement with reference vapour pressure data. Sample mass, heating rate, and use of inert diluents were important variables affecting accuracy of vapour pressure measurements.     

Effect of Pulsed Ultrasonic Field on the Filling of a Capillary with a Liquid

The filling of capillaries with liquids of various viscosity in the ultrasonic field is experimentally investigated. It is shown that the breakage of the meniscus and the fast intense dissolution of the gas that filled the capillary occur at the threshold switching-on of the ultrasonic field in low-viscosity liquids. This causes the residual (after switching-off of the ultrasound) filling of the capillaries with a low-viscosity liquid. It is established that the residual filling of capillaries is observed only with the pressure amplitudes P _m exceeding some critical value; the residual filling increases with P _m and disappears as cavitation is induced below the capillary end. It is shown that pulsed regime is optimal for the ultrasonication.     

Interfacial transport of evaporating water confined in nanopores

A semianalytical, continuum analysis of evaporation of water confined in a cylindrical nanopore is presented, wherein the combined effect of electrostatic interaction and van der Waals forces is taken into account. The equations governing fluid flow and heat transfer between liquid and vapor phases are partially integrated analytically, to yield a set of ordinary differential equations, which are solved numerically to determine the flow characteristics and effect on the resulting shape and rate of evaporation from the liquid-vapor interface. The analysis identifies three important parameters that significantly affect the overall performance of the system, namely, the capillary radius, pore-wall temperature, and the degree of saturation of vapor phase. The extension of meniscus is found to be prominent for smaller nanoscale capillaries, in turn yielding a greater net rate of evaporation per unit pore area. The effects of temperature and ambient vapor pressure on net rate of evaporation are shown to be analogous. An increase in pore-wall temperature, which enhances saturation pressure, or a decrease in the ambient vapor pressure result in enhancing the net potential for evaporation and increasing the curvature of the interface.     

Adsorption systems at temperatures below the freezing point of the adsorptive

Isothermal adsorption studies and the measurement of dimensional changes below the bulk freezing point of the adsorbate indicate that substances adsorbed in porous solids are unable to freeze in situ. The difference between the vapour pressure or free energy of the unfrozen adsorbate and that of the bulk adsorptive outside of the porous system is resolved by a desorption process; the desorbed matter freezes outside of the system while the vapour pressure of the adsorbate remaining in the pores decreases through meniscus formation. Mechanical breakdown of the system occurs only then, when this process cannot be completed and an equilibrium state is not attained.This mechanism was found to be valid for porous silica glass, hydrated cement paste, bricks, and even for biological substances such as animal and plant tissue, and foodstuff. This understanding has led to the development of new methods for testing the durability of building materials, clarification of some problems of the BET surface area determination method and it suggests an explanation for the action of cryoprotective agents.     

Capillary rise of a meniscus with phase change

The Lucas-Washburn equation, describing the motion of a liquid body in a capillary tube, is extended to account for the effect of phase change - evaporation or condensation. The system is found to always possess a stable equilibrium state when the temperature jump across the interface is confined to a certain range. We show that phase change affects the equilibrium height of the meniscus, the transition threshold from monotonic to oscillatory dynamics, and the frequency of oscillations, when present. At higher mass transfer rates and/or large capillary radii, vapor recoil is found to be the dominant factor. Evaporation lowers the equilibrium height, increases the oscillation frequency and lowers the transition threshold to oscillations. For condensation, two regimes are identified: at high mass transfer rates similar trends to those of evaporation are observed, whereas the opposite is found for low mass transfer rates, resulting in an increased equilibrium height, lower oscillation frequencies and a shift of the transition threshold toward monotonic dynamics.     

Characteristic features of the evaporation of liquids

Abstract

The evaporation rate variation of liquids (water, ethanol) is studied versus their vapour pressure. From measurements of liquid-vapour interface displacement versus time, the state change whose rate is v_o at initial time-is seen to slow down before reaching a constant rate v₁ under stationary working conditions. The difference between both rates increases as pressure decreases. In addition, whereas the v_o(P) curves are monotonous and increasing from saturation vapour pressure to vacuum, the v₁(P) curves have a typical shape, characterised by two extremums.

From the simultaneous measurement of temperature to assess the endothermic character of state change, it is shown that the previous observations may be related to the occurrence of a thermal flow at interface level.

The new profile of the v₁(P) curves can neither be predicted nor explained from conventional expressions of evaporations rate. The present paper shows that a thermodynamic interface model involving coupling of mass and heat flows allows the features detected to be accounted for with out any ambiguity.     

ZnP2晶体合成机理研究

在抽空密封石英管内放置元素锌和磷合成ZnP_2过程中, 仔细考察了不同升温程序的实验结果, 发现磷蒸汽压条件对于形成磷化物的性质相当重要, 在大于4大气压时会生成近100％黑色ZnP_2。用缩短合成时间,考察合成过程的中间产物, 以及用称量法、化学分析法和扫描电镜法对中间产物的分析, 提出了ZnP_2合成过程的主要机理。     

Kinetics and heats of sublimation and evaporation of 1,3,3-trinitroazetidine (TNAZ)

TNAZ (1,3,3-trinitroazetidine) is a relatively new, powerful, steam castable, strained ring explosive. Owing these characteristics it is of considerable interest to the energetic material community. A relatively high vapour pressure, volume contraction and formation of shrinkage cavities in the solidification of its melt may be considered as some of its disadvantages. The kinetics and heats of TNAZ sublimation and evaporation were studied by the non-isothermal and isothermal thermogravimetry method. The activation energy of 94-102 kJ mol^-1 was found for TNAZ sublimation, while the activation energy of 60-81 kJ mol^-1 was found for TNAZ evaporation. The enthalpy of TNAZ sublimation at the melting temperature was found to be 95 kJ mol^-1, and the enthalpy of TNAZ evaporation equals 66 kJ mol^-1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sample evaporation in conventional GC split/splitless injectors. Part 1: Some quantitative estimates concerning heat consumption during evaporation

During sample evaporation in conventional vaporizing injection, the supply of heat to the evaporating liquid is a problem, first because the amounts of heat consumed are relatively large and, secondly, because the heat must be transferred to the sample within a very short time. Times available for evaporation, required amounts of heat, possible sources of heat, and the time required to transfer the heat to the sample liquid are discussed. It is shown that mixing with carrier gas contributes little heat to the evaporation process, but also that packings with glass wool have too low a heat capacity to deliver the required amount of heat to the evaporating sample. Transfer of heat from the insert wall to the sample easily requires several seconds, even if cooling of the vaporizing zone by 20° is accepted. Thus “flash evaporation” is usually impossible and most liquids must be held in the vaporizing chamber to allow full evaporation.     

Effects of evaporation and melting on nonstoichiometry and inhomogeneity of LiInSe<Subscript>2</Subscript> crystals

Evaporation and compositional changes of the liquids above the melting point of LiInSe₂ crystals have been characterized quantitatively by using special techniques of a rapid thermal analysis and differential dissolution. The occurrence of a liquid immiscible region in the Li₂Se-rich side of the Li₂Se-In₂Se₃ diagram and incongruent evaporation with the preferential evaporation of In₂Se₃ rising markedly above boiling point were determined from the peaks on the thermal curves and from precise control over the composition of the vapour and residual solid as a function of temperature. It was shown that both the processes could be the sources of nonstoichiometry and inhomogeneity of the LiInSe₂ crystals.