Liquids and Solids

Youll Need to Know

the properties of liquids what is surface tension and what affects it the difference between cohesion and adhesion the properties of water the properties of solids what is vaporization what is condensation what is dynamic equilibrium and what affects it how to determine the heat of vaporization how to determine the boiling point how to read the critical point from a phase diagram how to read critical pressure from a phase diagram how to read critical temperature from a phase diagram what are supercritical fluids how to determine melting-freezing point what is supercooling what is sublimation how to draw and interpret a phase diagram

Properties of Liquids
All liquids have a definite volume but assume the shape of their container. Liquids have higher densities than gases and are only slightly compressible. The molecules slide past each other freely.

Surface Tension: The property of liquids arising from unbalanced molecular cohesive forces at or near the surface, as a result of which the surface tends to contract and has properties resembling those of a stretched elastic membrane. Cohesion: The intermolecular attraction between like molecules. Adhesion: The attraction between unlike molecules. Viscosity: A measure of a liquids resistance to flow. Example: cold maple syrup has a high viscosity.

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Properties of Water
The properties of water are (1) Excellent solvent for ionic compounds or other compounds capable of forming hydrogen bonds; (2) has a high specific heat due to hydrogen bonding, and therefore, water can absorb a substantial amount of heat while the temperature rises only slightly, which tends to stabilize global temperature; and (3) the liquid phase is more dense than the solid phase and results because water molecules are joined together in an extensive three-dimensional network in which each oxygen atom is tetrahedrally bonded to four hydrogen atomstwo by covalent bonds and two by hydrogen bonds.

Example
Q. Using principles of chemical bonding, explain why water is most dense at 4C, not 0C, its freezing point. A. Solid ice has a highly ordered three-dimensional structure, which keeps individual H2O molecules apart from each other and results in spaces (these spaces increase the volume and decrease the density). When heat is applied to ice, some of the H2O molecules have enough kinetic energy to break the hydrogen bonds and thereby separate from other H2O molecules in the lattice. These H2O molecules then become trapped in the spaces or cavities of the remaining three-dimensional ice structure. This results in more H2O molecules per unit of volume than previously (higher density). At this point, 4C, water is most dense. However, as the temperature increases (above 4C), two processes occur: (1) the entire three-dimensional structure collapses and the spaces diminish, which tends to increase density and (2) thermal expansion predominates and causes water to expand and become less dense.

Properties of Solids
All solids: (1) have a definite volume and shape, (2) are usually more dense than the liquid phase of the same substance, (3) are virtually incompressible, and (4) vibrate about fixed positions. Solids are either classified as (1) amorphous (e.g., glass), lacking any defined arrangement of its molecules or (2) crystalline (e.g., iron, table salt), the atoms, ions or molecules are in specific positions. The net attractive intermolecular forces in solids are at their maximum and result from either ionic forces, covalent bonds, van der Waals forces, hydrogen bonds, or combinations of any of these.

Phase Changes
Liquid-Vapor Equilibrium

Vaporization: A certain number of molecules at any temperature in a liquid possess enough kinetic energy to escape from the surface. In a closed system, these gaseous molecules exert a vapor pressure. Condensation: As the number of molecules increase in the vapor phase, some of them strike the surface of the liquid. Intermolecular forces between the molecules at the surface of the liquid and the gaseous molecule that strikes the surface cause the molecules to remain in the liquid phase.

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Dynamic equilibrium: Occurs when the rate of molecules leaving a liquid surface equals the rate of gaseous molecules returning to the liquid. The pressure at this point is called the equilibrium vapor pressure and is constant for any liquid at a given temperature l @ g. Equilibrium vapor pressures increase with temperature.

Heat of Vaporization and Boiling Point

Molar heat of vaporization (Hvap): The energy (kJ/mol) required to vaporize one mole of a liquid. Hvap is directly proportional to the strength of intermolecular forces of a liquid, which is reflected in its boiling point (stronger intermolecular forces ~ higher B.P.). Critical point: The temperature and pressure above which the liquid state can no longer exist. Critical pressure (Pc): The highest pressure at which a species can coexist as a liquid and a vapor. Critical temperature (Tc): The highest temperature at which a species can coexist as a liquid and a vapor. Supercritical fluid: A substance which is above its critical temperature and pressure.
supercritical fluid Pc critical point

liquid vapor
T

Tc

Liquid-Solid Equilibrium

Melting-freezing point: The melting point of a solid (which is the same temperature as the freezing point of a liquid) is the temperature at which both solid and liquid phases exist in equilibrium, l @ s. Normal refers to temperatures at 1 atm pressure. The energy required to melt one mole of a substance is called the molar heat of fusion (Hfus). The heat of fusion is always smaller than the heat of vaporization for a substance since when a liquid vaporizes, its molecules become completely separated from each other, and more energy is required to overcome these attractive intermolecular forces. When a solid melts to become a liquid, intermolecular forces do not need to be broken, only rearranged.

D - liquid gas condensation T (C) freezing melting B - solid/liquid A - solid Heat added over time C - liquid vaporization

E - gas

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Example
Q. Calculate the amount of energy (in kJ) needed to heat 100. grams of liquid water from 0C to 150C. The specific heat of water is 4.184 J/(g C), the molar heat of vaporization of water = 40.79 kJ/mol, and the specific heat of steam is 1.99 J/(g C). A. Break the problem into three parts: (1) Energy to heat water from 0C to 100C q1 = m c t = (100. g) (4.184 J/(g C)) (100C 0C) = 4.184 104 J = 41.8 kJ (2) Energy to vaporize 100. g of water at 100C 1 mol H 2 O q 2 = 100. g H 2 O # 18.02 g H O # 40.79 kJ = 226 kJ 1 mol H 2 O 2 (3) Energy to heat 100. g of steam from 100C to 150C q3= m $ c $ t = _100. g i_1.99 J/g $ cC i`150cC - 100cC j = 9.95 # 10 3 J = 9.95 kJ Now, add q1 + q2 + q3 for total amount of heat = 41.8 kJ + 226 kJ + 9.95 kJ = 278 kJ

Supercooling: Occurs when a liquid is temporarily cooled below its freezing point. This temporary condition occurs because not enough time has passed for the molecules in the liquid phase to arrange into an ordered solid. Sometimes, a seed crystal or gentle stirring will speed up solidification.

Solid-Vapor Equilibrium

Sublimation: The process by which molecules go directly from the solid into the gas phase (Example: dry ice, CO2). The reverse process whereby molecules go directly from the gas phase into the solid phase is known as deposition (Example: formation of frost). The energy required to sublime one mole of a substance is called the molar heat of sublimation (Hsub) and is the sum of the molar heat of fusion and molar heat of vaporization: Hsub = Hfus + Hvap

Phase Diagrams
Phase diagrams graphically show the overall relationships among the solid, liquid, and vapor phases and summarize the conditions at which a solid, liquid, or gas exist. They allow one to predict changes in the melting point and boiling point of substances as a result of changes in external pressure and to anticipate directions of phase transitions brought about by changes in temperature and pressure.

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melting freezing P (atm) solid

liquid

critical point vaporization

condensation sublimation deposition triple point gas

T (C)

Phase Diagram for H2O

liquid Pressure (atm) melting point Tm solid boiling point Tb

gas triple point 0 Temperature (C) For water, the liquid phase is more dense than the solid phase due to hydrogen bonding. 100 374

Example

1.5 P (atm) 1.0 0.5

10

30

50

70 90 T (C)

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Q. The normal boiling point of the substance represented by the phase diagram above is A. 15C B. 30C C. 70C D. greater than 70C E. cannot be determined from the diagram A. C. Normal boiling point is the temperature at which a liquids vapor pressure equals one atmosphere. Go up the Y axis to 1.0 atm, go straight across until you hit the liquid/gas equilibrium curvego straight down.

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