NORTHERN CARIBBEAN UNIVERSITY DEPARTMENT OF BIOLOGY and CHEMISTRY LECTURE NOTES CHEM122: GENERAL CHEMISTRY II Assistant Professor: Dr.

Nicole White
3. States of Matter

There are 3 states of matter (solid, liquid and gas) which are classified as such because of the interactions between the molecules found within the substance. For instance, in a solid the molecules are found packed tightly together with only a very small amount of kinetic energy compared to the intermolecular attraction. Solids are thus nearly incompressible and rigid and their molecules or ions are in close contact and do not move. For a liquid its molecules possess more kinetic energy and can move about relative to each other (called a fluid) but this kinetic energy is not enough to overcome the intermolecular attraction. Their molecules are more tightly packed. Liquids are relatively incompressible fluids. Gases too like liquids are fluid but they unlike liquids and solids possess a great amount of kinetic energy, enough to overcome any intermolecular attraction that might be present and so individual particles are able to move far away from each other. Gases are compressible fluids.

Each state of matter can be converted to another state by going through a phase transition a phase is a given state of either a substance or a solution; melting freezing, boiling condensing and sublimation deposition. A transfer of energy is required in all cases, endothermic or exothermic processes. Melting: change of a solid to a liquid. Freezing: change a liquid to a solid. Vaporization: change of a solid or liquid to a gas. Change of solid to vapor often called sublimation.

Condensation: change of a gas to a liquid or solid. Change of a gas to a solid often called deposition. Can you differentiate between the exothermic and endothermic processes? When a substance is heated, for example ice, first there is an increase in temperature with absorption of heat, however, at the melting point the temperature remains constant until all the ice has been melted to water. At this stage which is seen as a flat line on the heating curve the solid and liquid phases are in equilibrium. After complete fusion there is an increase in temperature which levels off again once the water and steam phases are in equilibrium.

Heat of vaporization: heat needed for the vaporization of a liquid. H2O(l) H2O(g) H = 40.7 kJ Heat of fusion: heat needed for the melting of a solid. H2O(s) H2O(l) H = 6.01 kJ Temperature does not change during the change from one phase to another.
Vapour pressure, P This is defined as the partial pressure of a vapour over the liquid measured at equilibrium at a given temperature. At any given temperature there will be some molecules within a liquid that possess enough kinetic energy to overcome the intermolecular attractions becoming a vapour. In a closed system the vapour molecules cannot move away from the liquid and in time the two will interact with the highly energetic gas molecules transferring energy to the less energetic liquid molecules resulting in condensation.

Initially the rate of vapourization is greater than that of condensation but given enough time the two rates be the same resulting in a dynamic equilibrium and it is at this point that the vapor pressure of the liquid can be determined. The differences in vapour pressure at different temperatures is due to the fact that at higher temperatures more molecules will have enough kinetic energy to overcome the intermolecular attractions and go into the vapour phase, the reverse is true for a decrease in temperature. Various liquids have differing vapour pressures due to differences in strengths of the intermolecular interactions that bind their molecules together the lower the vapour pressure the stronger the intermolecular forces.

In an open system, when the vapour pressure equals the atmospheric pressure the liquid begins to vapourize throughout resulting in bubbles and the liquid is said to be boiling. Normal boiling point the temperature at which the vapor pressure of a liquid is equal to atmospheric pressure (1 atm). The Clausius-Clapeyron equation shows how the vapor pressure and temperature are related. It can be written as: ln P = H vap R 1 +C T

R gas constant; C a constant that is characteristic of the liquid. A straight line plot results when ln P vs. 1/T is plotted and has a slope of Hvap/R. Clausius Clapeyron equation is true for any two pairs of points. Write the equation for each and combine to get: ln P2 H vap 1 1 = T T P1 R 1 2

Phase diagrams A phase diagram is a graphical way to summarize the conditions under which the different states of a substance are stable.

Graph of pressure-temperature relationship; describes when 1,2,3 or more phases are present and/or in equilibrium with each other. Lines indicate equilibrium state two phases. Triple point- Temp. and press. where all three phases co-exist in equilibrium. Critical temp.- Temp. where substance must always be gas, no matter what pressure. Critical pressure- vapor pressure at critical temp. Critical point- point where system is at its critical pressure and temp.

The sold lines represent the conditions of temperature and pressure at which equilibrium exists between the two phases on either side of the line. The normal melting and boiling points are those when the pressure is 1 atmosphere. These can be found from the phase diagram by drawing a line across at 1 atmosphere pressure. The line separating the solid and liquid phases is lightly affected by pressure as can be seen in the figure where only a small change in temperature is observed for a

large pressure change. Also, for most substances the line tends to lean to the right indicating that the solid is denser than the liquid. The opposite is seen as ice is less dense than water and so the phase boundary will lean towards the left. There is a point on the diagram at which all 3 phases are in equilibrium and this point is known as the triple point any temperature or pressure below this point finds only the solid and gaseous phases in equilibrium. The critical point, however, is where we have only 1 phase being stable as seen above for water only gas is observed. A supercritical fluid is formed when a substance is heated above its critical temperature whether or not it is at its critical pressure and has properties intermediate between those of a liquid and those of a gas. A. Liquids

Surface tension: This is the energy required to increase the surface area of a liquid by a unit amount. What is the theory behind this? Molecules in the bulk of a liquid experience no net attractive force as they are pulled on all sides by adjacent molecules. On the other hand, molecules on the surface experience a net pull toward the interior of the liquid making the surface tend to as small a surface area as possible and a substance does not penetrate it easily.

Viscosity: This is the resistance to flow that is exhibited by all liquids. In other words, if some liquid were poured on the floor, the easier it is for a liquid to spread out the less viscous it is. Consider water and mercury. Viscosity decreases as the temperature increases since increased temperatures tend to cause increased mobility of the molecule.

The terms explained above are dependent on the intermolecular attraction between molecules in a substance. This force of attraction can be used to explain not only viscosity and surface tension but also vapour pressure. Since compounds with large intermolecular forces have lower vapor pressures, we predict that one has to go to higher temperature to make them boil. So we can use the following principles to predict relative boiling points: Stronger intermolecular forces mean higher boiling points. Other things being equal: Polar molecules boil higher than nonpolar molecules. Hydrogen-bonded molecules boil higher than nonhydrogen-bonded molecules. Large molecules boil higher than small molecules.

Intermolecular forces There are 2 basic types of intermolecular attractions: van der Waals forces and hydrogen bonding. The former can be subdivided in dipole-dipole and London forces. Hydrogen bonding: this is a weak to moderate attractive force between a hydrogen atom covalently bonded to a very electronegative atoms, X, and a lone pair or electrons on another small, electronegative atom, Y. Hydrogen is usually bonded to O, N or F. Strongest of the intermolecular forces between neutral molecules. Dipole-dipole force: attractive force between polar molecules with positive end of one molecule is aligned with negative side of other. The strength of this intermolecular force depends on the size of the molecular dipole moment. It is approximately 5% as strong as H-bonding forces. London (dispersion) Forces: interactions between instantaneously formed electric dipoles on neighboring polar or nonpolar molecules. All molecules experience this type of intermolecular attraction. The more atoms there are in a molecule the greater the dispersion force. It is the weakest of the intermolecular forces. Approximately 1% as strong as dipole-dipole forces (except for large molecules where the forces can be comparable).

The below figure shows the higher boiling points of molecules that exhibit hydrogen bonding compared to compounds formed from elements from the same group with greater molecular weight.

B.

Solids

A nearly incompressible state of matter with a well defined shape. Types of solids: Crystalline a well defined arrangement of atoms; this arrangement is often seen on a macroscopic level. Ionic solids ionic bonds hold the solids in a regular three dimensional arrangement. Molecular solid solids like ice are held together by intermolecular forces. Covalent network a solid consists of atoms held together in large networks or chains by covalent networks. Metallic similar to covalent network except with metals. Provides high conductivity.

Amorphous atoms are randomly arranged. No order exists in the solid. These are normally formed when a pre-melted solid is cooled quickly so that the units cannot arrange themselves in an ordered state and are therefore random. The melting point of each solid is determined by the attractive forces acting within it whether they are inter- or intra-molecular. The strength of the attractive force can also determine certain physical properties of the solid such as electrical conductivity and hardness. Hardness The ability of the structural units within a solid to move with respect to each other is determined by the forces of attraction within said solid. If the attraction is strong then the solid will be quite hard and vice versa. Electrical conductivity in this instance the metallic solid would be the better conductor as its electrons are delocalized whilst in the other solid types the electrons are localized. In anionic liquid electricity is conducted via the ions. There are different types of crystals. Some examples are shown below. With sides a, b c abd angles , and . Side a is found opposite side and so on. Each of the below represent a unit cell which is a repeating unit in a crystal. Generally speaking, the lattice of the crystal is comprised of points at which an atom may be found. A scientific technique used to determine the structure of a crystal is X-ray diffraction: powder and crystal.

C.

Gases

Gases are known for their high kinetic energies and compressibility. They exert force (P = F A in kg/ms2 (Pa)) on objects they come into contact with and this pressure can be measured by a barometer or manometer.

The barometer measures the pressure of the atmospheric pressure and the monometer measures the pressure of a gas or liquid in a vessel.

Pressure can be expressed in many units: 1 atm (atmosphere) = 101325 Pa (Pascal) = 760 mmHg or torr. The SI units for pressure is Pascals.

Gas laws There are various gas laws that relate pressure, volume, temperature and moles. Boyles Law: this relates pressure and volume for a specific amount of gas at a fixed temperature. Around 1660 Robert Boyle was experimenting with the properties of gases under conditions where the temperature was held constants. He would take a sample of gas and measure the volume of the gas at different pressures (without changing the temperature). PV = constant

The value does not remain exactly constant with volume-pressure variations. The volume of a gas is inversely proportional to the pressure applied on it. deviates at high pressures. V 1 . This relationship, PV = constant, P

When considering 2 sets of pressure and volume data the following equation can be applied: P1V1 = P2V2. If 3 out of the four values are known then the equation can be manipulated so that the fourth can be determined. Charless law: this law relates volume to temperature for a given amount of gas at a fixed pressure. In 1787 French scientist Jacques Charles was studying the properties of gases at constant pressure. Charless law deviates at low temperature and high pressure. V = cons tan t T V1 V2 = T1 T2

also,

When the above gas laws are combined:

PV = cons tan t T

also,

P1V1 P2V2 = . T1 T2

Gay-Lussac's Law: At the beginning of the 19th century the French chemist Joseph Gay-Lussac made several contributions to the understanding of the properties of Gases. He did studies that were concerned the behavior of gases at constant volume. That is, how does the pressure depend on temperature if the volume is held constant? P = cons tan t T P1 P2 = T1 T2

also,

Gay-Lussac's Law of Combining Volumes: Gay-Lussac conducted other experiments and found that the ratio of the volumes of gases involved in chemical reactions (at the same temperature and pressure) were always simple fractions (fractions composed of small whole numbers).

For example, in the reaction

N2(g) + 3 H2(g) 2 NH3(g),

at constant temperature and pressure, Gay-Lussac found that the ratio of the volume of H 2(g) to the volume of N2(g) was always 3 to 1, regardless of the initial volumes used. Likewise, the ratio of the volume of H2(g) to the volume of NH3(g) was always 3 to 2. Avogadros law: states that equal volumes of any two gases at the same temperature and pressure contain the same number of molecules. One mole of gas contains the same number of molecules 6.02 1023 this volume is known as the molar gas volume, Vm = 22.4 L/mol at STP. STP standard temperature and pressure. The ideal gas law: An ideal gas is an idealized model for real gases that have sufficiently low densities. The condition of low density means that the molecules of the gas are so far apart that they do not interact (except during collisions that are effectively elastic). From the relationship Vm = cons tan t T finding the volume for n moles of gas the equation becomes PV = nRT. P

R gas constant = 0.0820578 Latm/Kmol = 0.0831451 Lbar/Kmol = 8.31451 J/Kmol., n number of moles. Gas Mixtures, Partial Pressures, and Dalton's Law: In a mixture of gases we speak of the total pressure of the gas mixture and the "partial pressures" of the individual gases in the mixture. The partial pressure of a gas in a mixture is defined as the pressure the gas would have (at the same temperature and in the same volume) if all the other component gases were removed leaving only the one gas. Dalton's law of partial pressures says that the total pressure of a gas mixture is the sum of all the partial pressures of all the gases in the mixture. If we number the gases as gas 1, gas 2, gas 3, and so on then, p = p1 + p2 + p3 + . . . . We can derive Dalton's law from the ideal g as law. Note that the n in P = nRT V

doesn't have any information about the identity of the gas and the equation is the same regardless of the identity of the gas. There is no reason why n couldn't be the sum of the number moles of each component in a gas mixture. That is, n = n1 + n2 + n3 + . . . . If we place this n into the ideal gas law we get,

which is Dalton's law.

Gas density The density of a gas can be determined by the relationship mass = moles molar mass. Density has the units g/cm3 or mass/volume and so manipulation of the ideal gas law gives: PV = nRT m RT V PM m = RT PM m = PV = m RT Mm

Kinetic Molecular Theory of Gases The kinetic molecular theory of gases states that all matter consists of extremely tiny particles that are in constant motion. In a solid the molecules are too close and too ordered and so dont have a lot of kinetic energy. These molecules can only vibrate. Liquid molecules have more kinetic energy

than solids but not enough to overcome the attractive forces between molecules and so the space between them is small. In gases, on the other hand, molecules have a large amount of kinetic energy and so are able to escape the attraction between molecules and travel great distances. All gas molecules have kinetic energy: E k =
1 2

mv 2 . The larger the mass the smaller the average speed.

This means that heavy gases are much slower than lighter ones.

There are five fundamental concepts of kinetic molecular theory. 1. A gas is composed of molecules whose size is much smaller than the distance between them. 2. Gas molecules move randomly in straight lines at various speeds and in every possible direction. 3. Except when gas molecules collide, forces of attraction and repulsion between them are negligible. 4. When collisions between molecules occur, they are elastic. Their kinetic energy remains constant. Gas molecules collide (elastically) with the walls of the container to produce a pressure, p. The molecules also collide with each other. Molecules do not lose or gain energy in their collisions with the walls or with each other. 5. The average kinetic energy of gas molecules is proportional to the absolute temperature.

Diffusion: This is the spread of gas molecules of one type through those of another type to occupy the space uniformly. If we release a small amount of ammonia gas in a quiet room (no air currents or turbulence or mixing) the ammonia will eventually spread throughout the room, due to the motion of the molecules. It may take several minutes to spread throughout the room because as it travels it collides with other gas molecules and changes direction constantly.

Effusion: This is the escape of gas molecules from a container through a tiny hole. The rate of effusion is inversely proportional to the square root of its molar mass at constant temperature and pressure. The rate at which a molecule diffuses through another gas is proportional to its average velocity. Thus the diffusion rate is inversely proportional to the square root of the formula weight. rate = 1 Mm

Effusion is dependent on the cross sectional area of the hole, the number of molecules per unit volume, and the average molecular speed. We will not need to know how to calculate absolute effusion rates in this course, but we will need to be able to calculate relative effusion rates. The ratio of the effusion rate of gas A (RateA) to the effusion rate of gas B (RateB) is, from the above discussion, rate A = rate B M mB M mA

4.

Analytical Chemistry

Analytical chemistry deals with the separation, identification and determination of components in a sample and consists of both qualitative and quantitative analyses. In carrying out quantitative analysis one must follow certain steps: 1. Method selection. 2. Sample acquisition and preparation.

3. Elimination of interference. 4. Measurement of analyte. 5. Calculation of results. 6. Determination of errors.

Method Selection: When choosing a method certain factors need to be taken into consideration, the first and most important being the level of accuracy required. Cost is another important factor as well as the number of samples that can be measured at any one time. Bearing all this in mind, it is a combination of these and other factors, the best compromise depending on the needs of the analyst, that influence the method chosen. Sample Acquisition and Preparation: The sample chosen must be representative of the bulk solution, sometimes referred as the stock in the case of solutions, first and foremost. Careful records must be kept of the source and history of the sample. In some cases, the sample may need to be ground into a suitable size, for a solid, or diluted in the case of a liquid sample. From each selected sample multiple measurements are carried out and so it is imperative that these replicate samples are treated identically. Elimination of Interference: Interference is any substance present in sample that might cause an error in the analysis of the analyte it affects an analytical signal or background. Measuring Analyte Calculation of Results Determination of Errors: As stated earlier proper records need to be taken in sample preparation and measurement and with this can the error or uncertainty associated with the final result can be determined. These errors can be obtained from the equipment used and a good understanding of errors is essential for any quantitative measurement and the reliability of the results reported. Scientists try to minimize the sources of errors as best they can and ensure that no source is

unaccounted for. This is an important area and will be dealt with in greater detail later in this course. Standard deviation (std. dev.) This is a measure of how closely replicate data cluster around the mean precision. Standard deviation can be applied to a population, , as well as to a sample of the population,s.

(x

)2

and

s=

(x

x) 2

N 1

xi ith value N number of values x sample mean population mean

The most common applications of standard deviations are associated with addition/subtraction and multiplication/division calculations. It is extremely important that you learn these. multiplication / division : y = a b c and y y = (a ) 2 + (b ) 2 + ( c ) 2 a b c

addition / subtraction : y = a + b c y = a 2 + b 2 + c 2