Top Document: Sci.chem FAQ - Part 5 of 7 Previous Document: News Headers Next Document: 20. Optical properties of chemicals See reader questions & answers on this topic! - Help others by sharing your knowledge 19.1 Rheological properties and terminology Contributed by Jim Oliver RHEOLOGY What is RHEOLOGY ? RHEOLOGY describes the deformation of a material under the influence of stresses. Materials in this context can be solids, liquids or gases. In this FAQ we will be concerned only with the rheological properties of liquids.[1] Perry discusses the some aspects of the behaviour of gases, and Ullmann discusses elastic solids. When liquids are subjected to stress they will deform irreversibly and flow. The measurement of this flow is the measurement of VISCOSITY. IDEAL liquids are very few, whereas non-ideal examples abound. Ideal liquids are : water and pure paraffin oil. Non-ideal examples would be toothpaste or cornflour mixed with a little water. [2] What is VISCOSITY ? VISCOSITY is expressed in Pascal seconds (Pa.s) and to be correct the conditions used to measure the VISCOSITY must be given. This is due to the fact that non-ideal liquids have different values of VISCOSITY for different test conditions of SHEAR RATE, SHEAR STRESS and temperature. [3,4] A graph describing a liquid subjected to a SHEAR STRESS (y axis) at a particular SHEAR RATE (x axis) is called a FLOW CURVE. The shape of this curve reveals the particular type of VISCOSITY for the liquid being studied. [3] What is a NEWTONIAN LIQUID ? NEWTONIAN LIQUIDS are those liquids which show a straight line drawn from the origin at 45 degrees, when graphed in this way. Examples of NEWTONIAN liquids are mineral oil, water and molasses. (Isaac NEWTON first described the laws of viscosity) [1] All the other types are NON NEWTONIAN. What does NON NEWTONIAN mean ? a. PSEUDOPLASTIC liquids are very common. These display a curve starting at the origin again and curving up and along but falling under the straight line of the NEWTONIAN liquid. In other words increasing SHEAR RATE results in a gradual decreasing SHEAR STRESS, or a thinning of viscosity with increasing shear. Examples are toothpaste and whipped cream. b. DILATANT liquids give a curve which curves under then upward and higher than the straight line NEWTONIAN curve. (Like a square law curve) Such liquids display increasing viscosity with increasing shear. Examples are wet sand, and mixtures of starch powder with small amounts of water. A car may be driven at speed over wet sand, but don't park on it, as the car may sink out of sight due to the lower shear forces (compared to driving over) the wet sand. There are other terms used which include : THIXOTROPY - this describes special types of PSEUDOPLASTIC liquids. In this case the liquid shows a YIELD or PLASTIC POINT before starting to thin out. What this means is the curve runs straight up the y axis for a short way then curves over following ( but higher and parallel to ) the PSEUDOPLASTIC curve. This YIELD POINT is time dependant. Some water based paints left overnight develop a FALSE BODY which only breaks down to become useable after rapid stirring. Also: the curve describing a THIXOTROPIC liquid will be different on the way up (increasing shear rate) to the way down (decreasing shear rate). The area inside these two lines is a measure of it's degree of THIXOTROPY. This property is extremely important in industrial products, e.g to prevent settling of dispersed solids on storage. [3] A RHEOPECTIC liquid is a special case of a DILATANT liquid showing increasing viscosity with a constant shear rate over time. Again, time dependant but in this case _increasing_ viscosity. Why do some liquids become solid ? A few special liquids (dispersions usually) display extraordinary DILATANT properties. A stiff paste slurry of maize or cornflour in water can appear to be quite liquid when swirled around in a cup. However on pouring some out onto a hard surface and applying extreme shear forces (hitting with a hammer) can cause a sudden increase in VISCOSITY due to it's DILATANCY. The VISCOSITY can become so high as to make it appear solid. The "liquid" then becomes very stiff for an instant and can shatter just like a solid material. It should be noted that the study of viscosity and flow behaviour is extremely complex. Some liquids can display more than one of the above properties dependant on temperature, time and heat history. What are Electrorheological Fluids? ( added by Bruce Hamilton ) Electrorheological (ER) fluids change their flow properties when an electric field is applied, and are usually dispersions of polarizable particles in an insulating base fluid [5]. Their apparent viscosity can change by orders of magnitude in milliseconds when a fews watts of electrical power are applied. The shear stress versus shear rate properties of ER fluids vary as a function of the applied electric field, When an electric field is applied, the fluid switches from a liquid to semisolid. The particles are usually irregularly- shaped 0.5-100um and present at concentrations of 10-40% by mass. ER fluids are dielectric particles in an insulating medium ( such as silicone oil ), along with additives ( such as surfactants, dispersants, and possibly a polar activator ). ER fluid effectively function as leaky capacitors. The electric field can be either AC, pulsed DC, or DC, with AC producing less electrophoresis of particles to electrodes. There are two categories of ER particulate materials, extrinsically polarizable materials ( which require a polar activator ), and intrinsically polarizable materials. Extrinsically polarizable materials can be polar nonionic compounds ( such as silica, alumina, or polysaccharides ), or polar ionic materials ( such as the lithium salt of polymethacrylic acid ), Intrinsically polarizable materials provide simpler systems - because a polar activator is not required, and they have a lower thermal coefficient of conductance. The most common examples are the ferroelectrics like barium titanate (BaTiO3 ) and polyvinylidene difluoride, however their performance has been poor, as has been that of metal powders ( such as iron and aluminium - even when coated with an insulating layer ), and research is concentrating on conducting polymers ( such as polyanilines and pyrolysed hydrocarbons ) [5,6]. The ability to utilise computer-based electrical switching to control ER fluid properties has resulted in vehicle suspension and industrial vibration control as major target applications for ER fluids. Demonstration systems have been built, and they match performance predictions, however cost and durability issues still have to be solved [7]. 19.2 Flammability properties and terminology There are several properties of flammable materials that are frequently reported. It should be remembered that most discussions concerning flammable liquids usually consider air as the oxidant, but oxygen and fluorine can also be used as oxidants for combustion, and they will result in very different values. The flammability limits in air are usually reported as the upper and lower limits ( in volume percent at a certain temperature, usually 25C ), and represent the concentration region that the vapour ( liquid HCs can not burn ) must be within to support combustion. Hydrocarbons have a fairly narrow range, ( n-hexane = 1.2 to 7.4 ), whereas hydrogen has a wide range ( 4.0 to 75 ). The minimum ignition energy is the amount of energy ( usually electrical ) required to ignite the flammable mixture. Some mixtures only require a very small amount of energy (eg hydrogen = 0.017mJ, acetylene = 0.017mJ ), whereas others require more (eg methanol = 0.14mJ, n-hexane = 0.29mJ, diethyl ether = 0.20mJ, acetone = 1.15mJ, dichloromethane = 133mJ @ 88C ), and some require significant amounts, (eg ammonia = >1000mJ ). The flash point is the most common measure of flammability today, especially in transportation of chemicals, mainly because most regulations use the flash point to define different classes of flammable liquids. The flash point of a liquid is the temperature at which the liquid will emit sufficient vapours to ignite when a flame is applied. The test consists of placing the liquid in a cup and warming it at a prescribed rate, and every few degrees applying a small flame to the air above the liquid until a "flash" is seen as the vapours burn. Note that the flame is not applied continuously, but is provided at prescribed intervals - thus allowing the vapour to accumulate. There are a range of procedures outlined in the standard methods for measuring flash point ( ASTM, ISO, IP ) and they have differing cup dimensions, liquid quantity, headspace volume, rate of heating, stirring speed, etc., but the most significant distinction is whether the space above the liquid is enclosed or open. If the space is enclosed, the vapours will be contained, and so the flash point is several degrees lower than if it is open. Most regulations specify closed-cup methods, either Pensky-Martens Closed Cup or Abel Closed Cup. It is important to remember that these methods are only intended for pure chemicals, if there is water or any other volatile non-flammable compounds present, their vapours can extinguish or mask the flash. For used lubricants, this may be partially overcome by using the TAG open cup procedure - which is slightly more tolerant of non-flammable vapours. A material can be flammable, but may not have a flash point if other non-flammable volatile compounds are present. For alkane hydrocarbons, flash point increases with molecular weight. There is an older measure, called the fire point, which is the temperature at which the liquid emits sufficient vapours to sustain combustion. The fire point is usually several degrees above the flash point for hydrocarbons. The minimum autoignition temperature is the temperature at which a material will autoignite when it contacts a surface at that temperature. The procedure consists of heating a glass flask and squirting small quantities of sample into it at various temperatures until the vapours autoignite. The only source of ignition is the heat of the surface. For the smaller hydrocarbons the autoignition temperature is inversely related to molecular weight, but it also increases with carbon chain branching. Autoignition temperature also correlates with gasoline octane ratings ( refer to Gasoline FAQ available in rec.autos.tech, which lists octane ratings and autoignition temperatures for a range of hydrocarbons.) Flash Point Autoignition Flammable Limits Temperature Lower Upper ( C ) ( C ) ( vol % at 25C) methane -188 630 5.0 15.0 ethane -135 515 3.0 12.4 propane -104 450 2.1 9.5 n-butane -74 370 1.8 8.4 n-pentane -49 260 1.4 7.8 n-hexane -23 225 1.2 7.4 n-heptane -3 225 1.1 6.7 n-octane 14 220 0.95 6.5 n-nonane 31 205 0.85 - n-decane 46 210 0.75 5.6 n-dodecane 74 204 0.60 - n-tetradecane 99 200 0.50 - 19.3 Supercritical properties and terminology? Supercritical fluids have some very unusual properties. When a compound is subjected to conditions around the critical point ( which is defined as the temperature at which the gas will not revert to a liquid regardless how much pressure is applied ), the properties of the supercritical fluid become very different to the liquid or the gas phases. In particular, the solubility behaviour changes. The behaviour is neither that of the liquid or that of the gas. The transition between liquid and gas can be completely smooth. The pressure-dependant densities and corresponding Hildebrand solubility parameters show no break on continuity as the supercritical boundary is crossed. Physical properties fall between those of a liquid and a gas. Diffusivities are approximately an order of magnitude higher than the corresponding liquid, while viscosities are an order of magnitude lower. These properties ( along with low surface tension ) allow SCFs to have liquid-like solvating power with the mass transport characteristics of a gas. Potential Supercritical Fluids Compound Critical Critical Density Temperature Pressure ( C ) ( bar ) (g cm^-3) Ammonia 132.4 112.8 0.235 Carbon dioxide 30.99 73.75 0.468 CFC-12 111.8 41.25 0.558 Dimethyl ether 126.9 52.7 0.271 Ethane 32.4 49.1 0.212 HCFC-22 96.15 49.90 0.524 HCFC-123 183.68 36.62 0.550 HFC-116 19.7 29.8 0.608 HFC-134a 101.03 40.57 0.508 Methanol 240.1 83.1 Nitrous oxide 36.4 72.54 0.453 Propane 96.8 42.66 0.225 Water 374.4 227.1 Xenon 16.6 58.38 1.105 Nitrous oxide is seldom used because early researchers reported explosions. Note that using liquid CO2 at pressure ( as for the commercial extraction of hops ) is still just liquid CO2 extraction, not supercritical CO2 extraction. There are several good general introductions to supercritical fluids [8,9,10] 19.4 Formation of gaseous bubbles in liquids Discussions about the behaviour of dissolved gases in liquids, especially when discussing carbonated beverages, are usually more appropriate in sci.physics and/or sci.mech.fluids, and there is a good text available [11]. Section 23.9 of this FAQ lists the change in solubility with temperature for common atmospheric gases in water at near-ambient pressure. As the temperature increases, the solubility decreases, creating a supersaturated solution that can result in bubble formation. A similar effect occurs if the pressure is reduced. The formation of bubbles can be understood in thermodynamic terms using the Gibbs free energy of the bubble. Gibbs free energy = -n * R * T ln(C/Cs) + gamma * A A = Surface area of the bubble. C = Concentration of gas in the liquid, Cs = Concentration of gas in the liquid at saturation, gamma = Interfacial tension between the gas and the liquid n = Number of moles of gas in the bubble = (P*V)/(R*T), where P = pressure, and V = volume of a sphere. R = Gas Constant T = Temperature After inserting the expressions for the surface area of a sphere (r = radius) and number of moles, and differentiating, then we obtain:- r(mininum) = 2 * gamma / ( P * ln(C/Cs)) This describes the size of a bubble that would continue to grow under the existing conditions, rather than redissolve. Of course, the expression assumes homogeneous precipitation of the bubble, and in real life most bubbles are created heterogeneously. Statistics and kinetics are also required to determine the rate of formation of bubbles, and predict the effect of changing parameters such as temperature. As the liquid is warmed, bubbles may be created faster, as the higher temperatures overcome the activation barrier - which is the difference between the Gibbs free energy when r is less than r(minimum), and the Gibbs free energy at r(minimum). The formation of a bubble also dramatically perturbs the system, even causing secondary bubbles to form. Secondary bubble formation may be implicated in the production of copious quantities of froth from shaken, quickly-opened, carbonated drink containers. The sites for gaseous bubble formation in supersaturated drinks are typically small particles, or minor flaws on the smooth surface of the container. 19.5 Why is Mercury a liquid at room temperature?. First, let's look at the melting points of some of the elements surrounding mercury in the periodic table ( in degrees C ) :- Period IB IIB IIIA 4s3d4p Cu 1083 Zn 419.5 Ga 29.8 5s4d5p Ag 960.8 Cd 320.9 In 157 6s(4f)5d6p Au 1063 Hg -38.4 Tl 304 The interesting comparison is between Hg and Au, as their properties differ dramatically, although their electron structures are similar:- 14 10 1 Au(g) : Xe | 4f , 5d , 6s 79 54 14 10 2 Hg(g) : Xe | 4f , 5d , 6s 80 54 Very few chemistry textbooks discuss relativistic effects on chemical properties, despite the availability of a comprehensive review by P.Pyykko [12]. There several good introductory articles on the derivation and calculation of various relativistic effects in molecules and atoms, so I'm not going to include details [13,14,15]. Suffice to say, that whilst smaller elements can treated simply, larger elements need treatment based on the Dirac equation, which shows that the s electrons are approaching the speed of light, consequently relativistic effects are important. If we take the relativistic mass of mercury (m);- Mo where m = -------------------- c (speed of light) = ~137 atomic units _____________ v = Z = 80 / ( v ) 2 Mo = rest mass / 1 - ( - ) \/ ( c ) The masses of the 1s electrons are increased by approximately 20% over their rest masses, which means that the radius is decreased by 20% - since mass appears in the denominator of Bohr radius calculations. All the other s shells also contract, with the 6s contracting ~14%, because their electron speeds near the nucleus are comparable, and the contraction of the inner part of the wave function also pulls in the outer tails. The p orbitals also contract a similar amount, and these contractions also results in increases the screening for d and f orbitals, which may then expand - about 3% for the 5d orbital of mercury. In mercury, the relativistically-contracted 6s2 orbital is full, thus the the two electrons do not contribute much to the metal-metal bond, which is not the situation for gold. The bonding in mercury is believed to be mainly van der Waals forces with a contribution from 6p orbital interaction. The relativistic contraction of the filled 6s2 orbital, when added to the contraction across the sixth row of the periodic table, results in relatively weak Hg-Hg bonds that are responsible for mercury being a liquid at room temperature. For those curious to know more, a recent article in J.Chem.Ed. provides much more detail and several good references [16]. Relativistic effects are also responsible for the colour of gold ( partially explained by the 5d -> 6s transition in gold requiring less energy than the 4d -> 5s transition in silver, resulting in a smaller d-s gap ) [12,14,16]. User Contributions:Top Document: Sci.chem FAQ - Part 5 of 7 Previous Document: News Headers Next Document: 20. Optical properties of chemicals Part1 - Part2 - Part3 - Part4 - Part5 - Part6 - Part7 - Single Page [ Usenet FAQs | Web FAQs | Documents | RFC Index ] Send corrections/additions to the FAQ Maintainer: B.Hamilton@irl.cri.nz
Last Update March 27 2014 @ 02:12 PM
|
Comment about this article, ask questions, or add new information about this topic: