States of Matter PDF

States of Matter Ronnel C. Garcia, RChE, RChT, RPh CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular...

States of Matter Ronnel C. Garcia, RChE, RChT, RPh CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Review of the States of Laws Liquid State and Matter Capillary Action The Solid State Phase Change and Phase Equilibrium  Review of the States of Matter Matter organizes into several phases or states CONTENTS based on its elements and external variables such as Review of the States of pressure and temperature. Matter Atoms constitute the three classical states of matter Intermolecular Forces (solid, liquid, and gas) under ordinary temperatures Gaseous State and Gas Laws and pressures. Liquid State and Complex molecules can also produce mesophases, Capillary Action such as liquid crystals, which exist between the The Solid State liquid and solid phases. Phase Change and Atoms become ionized when exposed to high Phase Equilibrium temperatures or intense electromagnetic fields, resulting in plasma.  Review of the States of Matter Gases, liquids and solids are all made up of CONTENTS microscopic particles, but the behaviors of these Review of the States of particles differ in the three phases. Matter In terms of Arrangement, particles in a: Intermolecular Forces gas are well separated with no regular arrangement. Gaseous State and Gas Laws liquid are close together with no regular arrangement. Liquid State and solid are tightly packed, usually in a regular pattern. Capillary Action In terms of Movement, particles in a: The Solid State gas vibrate and move freely at high speeds. Phase Change and liquid vibrate, move about, and slide past each other. Phase Equilibrium solid vibrate (jiggle) but generally do not move from place to place.  Review of the States of Matter Each state of matter is being affected by an CONTENTS intermolecular force Review of the States of For molecules to exist as aggregates in gases, Matter liquids, and solids, intermolecular forces must exist. Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Review of the States of Matter Melting: The transition from the solid to CONTENTS the liquid phase Review of the States of Freezing: The transition from the liquid Matter phase to the solid phase Intermolecular Forces Evaporation: The transition from the Gaseous State and Gas liquid phase to the gas phase Laws Condensation: The transition from the Liquid State and gas phase to the liquid phase Capillary Action The Solid State Sublimination: The transition from the Phase Change and solid phase to the gas phase Phase Equilibrium Deposition: The transition from the gas phase to the solid phase CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Intermolecular Forces Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Intermolecular Forces An intermolecular force (IMF) (or secondary force) is CONTENTS the force that mediates interaction between Review of the States of molecules, including the electromagnetic forces of Matter attraction or repulsion which act between atoms Intermolecular Forces and other types of neighboring particles, e.g. atoms Gaseous State and Gas or ions. Laws Liquid State and Intermolecular forces are weak relative to Capillary Action intramolecular forces – the forces which hold a The Solid State molecule together. Phase Change and Intermolecular forces are repulsive at short Phase Equilibrium distances and attractive at long distances.  Intermolecular Forces Attractive intermolecular forces are categorized into CONTENTS the following types: Review of the States of Hydrogen bonding Matter Ion–dipole forces and ion–induced dipole force Intermolecular Forces Cation–π, σ–π and π–π bonding Gaseous State and Gas Van der Waals forces – Keesom force, Debye force, and Laws London dispersion force Liquid State and Cation–cation bonding Capillary Action Salt bridge The Solid State Phase Change and Each Intermolecular Force will be discussed in detail Phase Equilibrium in Lesson 3  Intermolecular Forces Information on intermolecular forces is obtained by CONTENTS macroscopic measurements of properties like Review of the States of viscosity, pressure, volume, temperature Matter Intermolecular Forces refers to interactions Intermolecular Forces between any particles (molecules, atoms, ions, and Gaseous State and Gas Laws molecular ions) that do not result in the creation of Liquid State and chemical bonds, such as ionic, covalent, or metallic. Capillary Action Cohesion, or the attraction of like molecules, and The Solid State Adhesion, or the attraction of unlike molecules, are Phase Change and manifestations of intermolecular forces Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Gaseous State and Gas Laws Liquid State and Laws Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A gas is a compressible fluid. A gas will conform to CONTENTS the geometry of its container while also expanding Review of the States of to fill it. Matter In a gas, the molecules have enough kinetic energy Intermolecular Forces to minimize the influence of intermolecular forces, Gaseous State and Gas Laws and the average distance between nearby Liquid State and molecules is substantially larger than the molecular Capillary Action size. The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A gas can also be called as a vapor at temperatures CONTENTS below its critical temperature, can be liquefied by Review of the States of compression alone, without the need for cooling. Matter When a vapor is in equilibrium with a liquid (or Intermolecular Forces solid), the gas pressure equals the liquid's vapor Gaseous State and Gas Laws pressure. Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Elemental Gases CONTENTS The only chemical elements that are stable diatomic Review of the States of homonuclear molecular gases at STP are Matter hydrogen (H2) Intermolecular Forces nitrogen (N2) Gaseous State and Gas oxygen (O2) and two halogens: fluorine (F2) and chlorine (Cl2). Laws Liquid State and There are also monatomic noble gases Capillary Action helium (He) neon (Ne) The Solid State argon (Ar) Phase Change and krypton (Kr) Phase Equilibrium xenon (Xe) radon (Rn)  Gaseous State and Gas Laws Compared to the other states of matter, gases have CONTENTS low density and viscosity. Pressure and Review of the States of temperature influence the particles within a certain Matter volume. This variation in particle separation and Intermolecular Forces speed is referred to as compressibility. Gaseous State and Gas Laws Gas particles spread apart or diffuse in order to Liquid State and homogeneously distribute themselves throughout Capillary Action any container. The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws In the assay of ethyl nitrite spirit, the nitric oxide gas that is liberated from a definite quantity of spirit and collected in a gas burette occupies a volume of CONTENTS 30.0ml at a temperature of 20°C and a pressure of 740mmHg. What is the volume Review of the States of at 0°C and 760mmHg? Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws What is the temperature of an 11.2-L sample of carbon monoxide, CO, at 744 torr if it occupies 13.3 L at 55 °C and 744 torr? CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A 2.50-L volume of hydrogen measured at –196 °C is warmed to 100 °C. Calculate the volume of the gas at the higher temperature, assuming no change in pressure. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A balloon inflated with three breaths of air has a volume of 1.7 L. At the same temperature and pressure, what is the volume of the balloon if five more same- CONTENTS sized breaths are added to the balloon? Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws How many grams of gas are present in each of the following cases? CONTENTS 0.100 L of CO2 at 307 torr and 26 °C 8.75 L of C2H4, at 378.3 kPa and 483 K Review of the States of 221 mL of Ar at 0.23 torr and –54 °C Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A high-altitude balloon is filled with 1.41 × 104 L of hydrogen at a temperature of 21 °C and a pressure of 745 torr. What is the volume of the balloon at a height of 20 CONTENTS km, where the temperature is –48 °C and the pressure is 63.1 torr? Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Ideal Gas Law CONTENTS Assumptions of the Ideal Gas Law The particles have no forces acting among them Review of the States of These particles do not take up any space, meaning their atomic Matter volume is completely ignored. Intermolecular Forces Gaseous State and Gas An ideal gas is a hypothetical gas dreamed by chemists Laws because it would be much easier if things like intermolecular forces do not exist to complicate the simple Ideal Gas Law Liquid State and Capillary Action We must emphasize that this gas law is ideal. As students, The Solid State professors, and chemists, we sometimes need to understand Phase Change and the concepts before we can apply it, and assuming the gases are in an ideal state where it is unaffected by real world Phase Equilibrium conditions will help us better understand the behavior the gases. For a gas to be ideal, its behavior must follow the Kinetic-Molecular Theory whereas the Non-Ideal Gases will deviate from this theory due to real world conditions.  Gaseous State and Gas Laws Derivation of Ideal Gas Law CONTENTS ᵄᵄ=ᵅᵄᵄ Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Values of R CONTENTS Value of R WILL change when dealing with different unit Review of the States of of pressure and volume (Temperature factor is Matter overlooked because temperature will always be in Kelvin Intermolecular Forces instead of Celsius when using the Ideal Gas equation) Gaseous State and Gas Values of R Laws 0.082057 L atm mol-1 K-1 Liquid State and 62.364 L Torr mol-1 K-1 Capillary Action 8.3145 m3 Pa mol-1 K-1 The Solid State 8.3145 J mol-1 K-1* Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws What is the density of nitrogen gas (ᵄ 2) at 248.0 Torr and 18°C? CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Find the volume, in mL, when 7.00 g of O2 and 1.50 g of Cl2 are mixed in a container CONTENTS with a pressure of 482 atm and at a temperature of 22º C. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Real Gas CONTENTS Real gases are nonideal gases whose molecules occupy Review of the States of space and have interactions; consequently, they do not adhere to the ideal gas law. Matter To understand the behavior of real gases, the following Intermolecular Forces must be considered: Gaseous State and Gas compressibility effects; Laws variable specific heat capacity; Liquid State and van der Waals forces; non-equilibrium thermodynamic effects; Capillary Action issues with molecular dissociation and elementary reactions The Solid State with variable composition Phase Change and For most applications, such a detailed analysis is Phase Equilibrium unnecessary, and the ideal gas approximation can be used with reasonable accuracy. On the other hand, real gas models have to be used near the condensation point of gases, near critical points, at very high pressures  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws In an industrial process, nitrogen is heated to 500 K at a constant volume of 1.000 cubic meters. The gas enters the container at 300 K and 100 atm. The mass of the CONTENTS gas is 92.4 kg. Use the van der Waals equation to determine the approximate Review of the States of pressure of the gas at its working temperature of 500 K. For nitrogen, a = 1.352 ᵅᵅ6 ᵄᵆᵅ ᵅᵅᵅ − 2, b = 0.0387 ᵅᵅ3 ᵅᵅᵅ − 1 Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Compute for the partial pressure Ne, Ar and Xe if the total pressure is 2.0atm and Ne is 4.46 moles, Ar is 0.74 moles and Xe is 2.15 moles. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A mixture of hydrogen gas and oxygen gas exerts a total pressure of 1.5 atm on the walls of its container. If the partial pressure of hydrogen is 1 atm, find the mole CONTENTS fraction of oxygen in the mixture. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws At a temperature of 300K, 30 liters of gas A kept under pressure of 1 atm and 15 liters of gas B kept under pressure of 2 atm is transferred into an empty 10L CONTENTS container. Calculate the total pressure inside the container and the partial pressures Review of the States of of gas A and gas B (Assume that A and B are ideal gases). Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws If fluorine gas diffuses at a rate of 363 m/s at a certain temperature, what is the rate of diffusion of neon gas at the same temperature? CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A gas mixture of helium, oxygen, and nitrogen is contained in a 150L container. Find the relative rate of diffusion of the helium compared to nitrogen. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Liquid State and Capillary Laws Liquid State and Action Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws A liquid is a nearly incompressible fluid that adapts to CONTENTS the shape of its container while maintaining a (nearly) Review of the States of constant volume regardless of pressure. If the Matter temperature and pressure are constant, the volume is Intermolecular Forces determined. Gaseous State and Gas Intermolecular (or interatomic, or interionic) forces Laws remain essential, but the molecules have enough energy Liquid State and to move relative to one another, and the structure is Capillary Action mobile. The Solid State This means that the shape of a liquid is not fixed and is Phase Change and determined by its container. Phase Equilibrium The volume is typically greater than that of the corresponding solid, with the best-known exception being water. A liquid's critical temperature is the greatest temperature it can exist at.  Gaseous State and Gas Laws The density of a liquid is usually close to that of a CONTENTS solid, and much higher than that of a gas. Therefore, Review of the States of liquid and solid are both termed condensed matter. Matter On the other hand, as liquids and gases share the Intermolecular Forces ability to flow, they are both called fluids. Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws For Liquids, Capillary action is the process by which CONTENTS a liquid flows in a confined space against or in the Review of the States of absence of external forces such as gravity. Matter It is caused by intermolecular interactions between Intermolecular Forces the liquid and the surrounding solid surfaces. Gaseous State and Gas Laws If the tube's diameter is small enough, surface Liquid State and tension (produced by cohesion within the liquid) Capillary Action and adhesion forces between the liquid and The Solid State container wall combine to propel the liquid. Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Jurin’s Law CONTENTS Jurin's law, or capillary rise, is the simplest analysis Review of the States of of capillary action (the induced motion of liquids in Matter small channels) Intermolecular Forces Gaseous State and Gas Jurin’s law states that the maximum height of a Laws liquid in a capillary tube is inversely proportional to Liquid State and the tube's diameter. Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the height to which water will rise in a capillary tube of radius 0.5 mm0.5mm. The surface tension of water is 0.072 N/m, the density of water is CONTENTS 1000 kg/cu.m., and the contact angle is 0∘. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the height to which mercury will fall in a capillary tube of radius 0.3 mm. The surface tension of mercury is 0.485 N/m, the density of mercury is CONTENTS 13534 kg/cu.m., and the contact angle is 140∘. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the surface tension of water if it rises to a height of 45 mm in a capillary tube with a radius of 0.4 mm. The density of water is 1000 kg/m3, and the contact CONTENTS angle is 0∘. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the surface tension of ethanol if it rises to a height of 20 mm in a capillary tube with a radius of 0.25 mm. The density of ethanol is 0.789 g/mL, and the CONTENTS contact angle is 0∘. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas The Solid State Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  The Solid State In a solid, the molecules are closely packed CONTENTS together, resulting in the least amount of kinetic Review of the States of energy compared to the other states. Matter This dense molecular arrangement imparts Intermolecular Forces structural rigidity to solids, making them resistant to Gaseous State and Gas Laws forces applied to their surfaces. Liquid State and The characteristic properties of solids include: Capillary Action Structural Rigidity: Solids maintain a fixed shape and The Solid State volume, unlike liquids and gases that conform to the Phase Change and shape of their container. Phase Equilibrium Resistance to Deformation: Due to the tight molecular packing, solids exhibit significant resistance to external forces, ensuring they maintain their form under various conditions.  The Solid State Molecular Arrangement in Solids CONTENTS Crystalline Solids: Crystalline solids have an ordered and repeating atomic structure. Review of the States of Physical Properties: High melting points, distinct geometric shapes, Matter and anisotropy (direction-dependent properties). Pharmaceutical Relevance: Crystalline forms of drugs often exhibit Intermolecular Forces higher stability and predictability in dissolution rates. For example, Gaseous State and Gas the crystalline form of a drug like aspirin can be more stable and have a longer shelf life compared to its amorphous form. Laws Examples: Sodium chloride, diamond. Liquid State and Amorphous Solids: Capillary Action Lack long-range order; atoms or molecules are arranged randomly. The Solid State Physical Properties: Lower melting points, isotropic properties (same in all directions), and typically less stable than crystalline Phase Change and counterparts. Pharmaceutical Relevance: Amorphous forms of drugs can dissolve Phase Equilibrium more quickly than crystalline forms, leading to potentially higher bioavailability. For instance, amorphous forms of drugs like indomethacin can enhance solubility and absorption. Examples: Glass, some polymers.  The Solid State Types of Solids: CONTENTS Ionic Solids: Comprised of ions held together by strong Review of the States of electrostatic forces. They typically have high melting points and are hard and brittle (e.g., NaCl). Matter Covalent Network Solids: Consist of atoms connected by Intermolecular Forces covalent bonds in a continuous network, making them Gaseous State and Gas very hard and with high melting points (e.g., diamond, Laws silicon carbide). Liquid State and Metallic Solids: Feature a sea of delocalized electrons Capillary Action that provide metallic bonding, resulting in good electrical and thermal conductivity and malleability (e.g., iron, The Solid State gold). Phase Change and Molecular Solids: Held together by intermolecular forces Phase Equilibrium such as Van der Waals forces, dipole-dipole interactions, and hydrogen bonds. They generally have lower melting points (e.g., ice, dry ice). CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Phase Change and Phase Laws Liquid State and Equilibrium Capillary Action The Solid State Phase Change and Phase Equilibrium  Phase Change and Phase Equilibrium Phase Change CONTENTS A phase change, or phase transition, is the Review of the States of transformation of a substance from one state of matter Matter to another. Intermolecular Forces Common phase changes include melting, freezing, Gaseous State and Gas vaporization, condensation, sublimation, and Laws deposition. Liquid State and Melting (Fusion): Transition from solid to liquid. Freezing (Solidification): Transition from liquid to solid. Capillary Action Vaporization (Boiling/Evaporation): Transition from liquid to The Solid State gas. Phase Change and Condensation: Transition from gas to liquid. Phase Equilibrium Sublimation: Transition from solid to gas without passing through the liquid phase. Deposition: Transition from gas to solid without passing through the liquid phase.  Phase Change and Phase Equilibrium Phase Change CONTENTS Each phase change involves energy exchange, Review of the States of typically in the form of heat. Matter Intermolecular Forces During a phase change, the temperature of the Gaseous State and Gas substance remains constant until the transition is Laws complete. Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Phase Change and Phase Equilibrium Phase Change and Heat CONTENTS Heat is the energy transferred between systems due Review of the States of to temperature differences. Matter Intermolecular Forces In phase changes, heat is used to overcome Gaseous State and Gas intermolecular forces: Laws Latent Heat: The heat absorbed or released during a Liquid State and phase change at constant temperature. Capillary Action Enthalpy of Fusion (Δᵃᵅ): Heat required to melt a solid. The Solid State Enthalpy of Vaporization (Δᵃ vap): Heat required to Phase Change and vaporize a liquid. Phase Equilibrium Enthalpy of Sublimation (Δᵃ sub): Heat required to sublimate a solid  Phase Change and Phase Equilibrium Heat Capacity CONTENTS Heat capacity is the amount of heat required to change Review of the States of the temperature of a substance by 1°C (or 1 K). Matter It is an important concept for understanding how Intermolecular Forces substances absorb and release heat. Gaseous State and Gas Laws Specific Heat Capacity (ᵅc): Heat capacity per unit mass. Liquid State and ᵅ=ᵅ⋅ᵅ⋅Δᵄ Capillary Action ᵅ: Heat energy. The Solid State Phase Change and ᵅ: Mass of the substance. Phase Equilibrium ᵅ: Specific heat capacity. Δᵄ: Change in temperature.  Phase Change and Phase Equilibrium Heat Required for Phase Change CONTENTS The heat required to change the phase of a Review of the States of substance is given by: Matter Intermolecular Forces ᵅ=ᵅ⋅Δᵃ Gaseous State and Gas ᵅ: Heat energy. Laws Liquid State and ᵅ: Mass of the substance. Capillary Action Δᵃ : Enthalpy change (fusion, vaporization, or The Solid State sublimation) Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the heat required to melt 100 g of ice at 0°C. The enthalpy of fusion of ice is 334 J/g. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Determine the amount of heat required to raise the temperature of 200 g of water from 20°C to 80°C. The specific heat capacity of water is 4.18 J/g·°C. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws You have 200 g of ice at -10°C, and you want to heat it to 10°C. First, the ice must be warmed to 0°C, then melted, and finally the resulting water must be heated to CONTENTS 10°C. Given the following data: Review of the States of Specific heat capacity of ice: 2.09 J/g·°C Matter Enthalpy of fusion of ice: 334 J/g Intermolecular Forces Specific heat capacity of water: 4.18 J/g·°C Gaseous State and Gas Calculate the total amount of heat required. Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws You have 300 g of water at 50°C, which you need to cool to -5°C. First, the water must be cooled to 0°C, then frozen, and finally the ice must be cooled to -5°C. CONTENTS Given the following data: Review of the States of Specific heat capacity of water: 4.18 J/g·°C Matter Enthalpy of fusion of water: 334 J/g Intermolecular Forces Specific heat capacity of ice: 2.09 J/g·°C Gaseous State and Gas Calculate the total amount of heat removed. Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Calculate the heat required to heat 150 g of ethanol from 20°C to its boiling point (78°C) and then to vaporize it. CONTENTS Given the following data: Review of the States of Specific heat capacity of ethanol: 2.44 J/g·°C Matter Enthalpy of vaporization of ethanol: 38.56 kJ/mol Intermolecular Forces Molar mass of ethanol (C₂H₅OH): 46.07 g/mol Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Phase Change and Phase Equilibrium Phase Equilibrium CONTENTS Phase equilibrium occurs when multiple phases of a Review of the States of substance coexist in balance, with no net change in Matter the amount of each phase over time. Intermolecular Forces Gaseous State and Gas It is described by the Gibbs phase rule and phase Laws diagrams. Liquid State and ᵃ=ᵃ−ᵄ+2 Capillary Action The Solid State ᵃ : Degrees of freedom (number of independent Phase Change and variables like temperature and pressure). Phase Equilibrium ᵃ: Number of components. ᵄ: Number of phases present.  Phase Change and Phase Equilibrium Phase Equilibrium CONTENTS Liquid-Vapor Equilibrium: When a liquid and its Review of the States of vapor coexist at a constant temperature and Matter pressure. Intermolecular Forces Gaseous State and Gas Solid-Liquid Equilibrium: When a solid and liquid Laws phase are in equilibrium at a given temperature and Liquid State and pressure. Capillary Action The Solid State Phase Change and Phase Equilibrium  Phase Change and Phase Equilibrium CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws Consider a single-component system (e.g., water) with two phases (liquid and vapor) in equilibrium. Calculate the number of degrees of freedom. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws In a binary system (two components) with three phases (solid, liquid, gas) present, determine the degrees of freedom. CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Gaseous State and Gas Laws In a binary alloy system, the overall composition of the mixture is 30% A and 70% B. The compositions of phase A and phase B are 20% A and 80% A, respectively. CONTENTS Calculate the fraction of each phase present in equilibrium. Review of the States of Matter Intermolecular Forces Gaseous State and Gas Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium  Summary States of Matter: CONTENTS Solid: Fixed shape and volume, particles are closely packed in a regular pattern. Minimal particle motion. Review of the States of Matter Liquid: Fixed volume but takes the shape of its container, particles are close but can move past each other. Intermolecular Forces Gas: No fixed shape or volume, particles are far apart and move freely. Gaseous State and Gas Plasma: Ionized gas with free electrons, found in stars and fluorescent Laws lights. Liquid State and Capillary Action Intermolecular Forces The Solid State Types of Intermolecular Forces: Phase Change and Van der Waals Forces: Weak interactions including dipole-dipole, dipole-induced Phase Equilibrium dipole, and London dispersion forces. Hydrogen Bonds: Strong type of dipole-dipole interaction involving hydrogen atoms bonded to electronegative atoms like O, N, or F. Ionic Bonds: Attraction between oppositely charged ions.  Summary Gaseous State and Gas Laws CONTENTS Gas Laws: Boyle’s Law: (at constant T). Review of the States of Charles’s Law: (at constant P). Matter Avogadro’s Law: (at constant P and T). Intermolecular Forces Ideal Gas Law: PV=nRT Gaseous State and Gas Laws Liquid State and Liquid State and Capillary Action Properties of Liquids: Capillary Action Viscosity: Resistance to flow. The Solid State Surface Tension: Energy required to increase the surface area of a liquid. Phase Change and Capillary Action: Ability of a liquid to flow in narrow spaces against gravity. Phase Equilibrium  Summary The Solid State CONTENTS Types of Solids: Crystalline Solids: Regular, repeating pattern (e.g., salts, metals). Review of the States of Amorphous Solids: No long-range order (e.g., glass, some polymers). Matter Intermolecular Forces Gaseous State and Gas Phase Changes: Laws Melting: Solid to liquid. Freezing: Liquid to solid. Liquid State and Vaporization: Liquid to gas. Capillary Action Condensation: Gas to liquid. The Solid State Sublimation: Solid to gas without passing through the liquid state. Phase Change and Phase Equilibrium Phase Equilibrium: Describes the balance between different phases at certain temperatures and pressures (e.g., equilibrium between liquid and vapor in a closed container). CONTENTS Review of the States of Matter Intermolecular Forces Gaseous State and Gas Thank You! Laws Liquid State and Capillary Action The Solid State Phase Change and Phase Equilibrium Laws of Thermodynamics Ronnel C. Garcia, RChE, RChT, RPh CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Zeroth Law of Second Law of Thermodynamics Thermodynamics Third Law of Thermodynamics  Zeroth Law of Thermodynamics The Zeroth Law of Thermodynamics states that if CONTENTS two thermodynamic systems are each in thermal Zeroth Law of equilibrium with a third system, they are in Thermodynamics thermal equilibrium with each other. First Law of This law establishes the concept of temperature and Thermodynamics Second Law of is fundamental to the definition of temperature in Thermodynamics thermodynamics. Third Law of Thermodynamics  Zeroth Law of Thermodynamics Importance of the Zeroth Law of Thermodynamics in CONTENTS Pharmacy Temperature Measurement and Control: Precise temperature Zeroth Law of control is crucial in pharmaceutical processes, including the Thermodynamics manufacturing, storage, and transportation of drugs. Ensuring First Law of that medications are kept at the correct temperature prevents degradation and ensures efficacy. Thermodynamics Stability Testing: The Zeroth Law is vital in the stability testing Second Law of of pharmaceuticals. Drugs must be tested for stability at Thermodynamics different temperatures to determine their shelf life and Third Law of appropriate storage conditions. Chemical Reactions and Formulations: Many pharmaceutical Thermodynamics processes involve chemical reactions that are temperature- dependent. Understanding and controlling these temperatures ensure the reactions proceed correctly, yielding the desired products.  Zeroth Law of Thermodynamics Thermal Equilibrium CONTENTS If 𝑇𝐴 = 𝑇𝐶 and 𝑇𝐵 = 𝑇𝐶 Zeroth Law of Then Thermodynamics First Law of 𝑇𝐴 = 𝑇𝐵 Thermodynamics Examples: Second Law of A thermometer is used to measure the temperature of a Thermodynamics beaker of water. The thermometer shows a reading of Third Law of 25∘𝐶. By the Zeroth Law, since the thermometer and the water are in thermal equilibrium, the temperature of the Thermodynamics water is 25∘𝐶 A drug storage room has a temperature monitoring system that shows a temperature of 20∘𝐶. A new batch of drugs is brought in and left to equilibrate. By the Zeroth Law, after sufficient time, the drugs will be at the same temperature as the room, which is 20∘𝐶 CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics First Law of Second Law of Thermodynamics Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics The First Law of Thermodynamics, also known as CONTENTS the Law of Conservation of Energy, states that Zeroth Law of energy cannot be created or destroyed, only Thermodynamics transformed from one form to another. First Law of Mathematically, it is expressed as: Thermodynamics Second Law of Δ𝑈=𝑄−𝑊 Thermodynamics Where: Third Law of Thermodynamics Δ𝑈 is the change in the internal energy of the system. 𝑄 is the heat added to the system. 𝑊 is the work done by the system  First Law of Thermodynamics q is positive if the heat is taken up by the system CONTENTS (i.e., energy is gained by the system). Zeroth Law of w is positive if work is done by the system (i.e., Thermodynamics energy is lost by the system). First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Importance of the First Law of Thermodynamics in CONTENTS Pharmacy Zeroth Law of Drug Manufacturing Processes: Understanding energy Thermodynamics changes during reactions and processes, such as mixing, First Law of heating, or cooling, is crucial for optimizing pharmaceutical manufacturing. Thermodynamics Second Law of Thermodynamic Stability: Helps in studying the stability Thermodynamics of drugs under various temperature and pressure conditions, ensuring that they remain effective Third Law of throughout their shelf life. Thermodynamics Bioenergetics: Understanding the energy transformations in biological systems aids in the design of drugs that can interact effectively with biological pathways.  First Law of Thermodynamics Work: CONTENTS Work is done by a gas when it expands against a Zeroth Law of resisting pressure, as happens when a piston moves Thermodynamics in a cylinder First Law of 𝑊 = 𝑃Δ𝑉 Thermodynamics Second Law of where ΔV is the volume displaced. Thus work of Thermodynamics expansion is the product of the (constant) pressure Third Law of and the volume change; in fact, this is often refer to Thermodynamics work of expansion  First Law of Thermodynamics Work: CONTENTS Now suppose that the gas is ideal and that the Zeroth Law of process is carried out isothermally. From the ideal Thermodynamics gas law, PV = nRT First Law of 𝑉2 Thermodynamics 𝑊 = 𝑛𝑅𝑇 𝑙𝑛 Second Law of 𝑉1 Thermodynamics Third Law of If V2 > V1, the system does work on the Thermodynamics surroundings, and w is positive. If V1 > V2, the surroundings do work on the system, and w is negative.  First Law of Thermodynamics Enthalpy CONTENTS When a chemical process is carried out at constant Zeroth Law of pressure, the heat evolved or absorbed, per mole, Thermodynamics can be identified as ΔH. Specific symbols and names First Law of have been devised to identify ΔH with particular Thermodynamics Second Law of processes. Thermodynamics For example, the heat absorbed by a solid on melting is called the heat of fusion and is labeled ΔHm or ΔHf Third Law of Thermodynamics The heat of solution is the enthalpy change per mole when a solute dissolves in a solvent For a chemical reaction ΔH is called a heat of reaction. The heat of reaction may be positive (heat is absorbed) or negative (heat is evolved).  First Law of Thermodynamics Internal Energy CONTENTS Internal energy is defined as the energy associated with Zeroth Law of the random, disordered motion of molecules. Thermodynamics It is separated in scale from the macroscopic ordered energy associated with moving objects; it refers to the First Law of invisible microscopic energy on the atomic and Thermodynamics molecular scale. Second Law of For example, a room temperature glass of water sitting Thermodynamics on a table has no apparent energy, Third Law of either potential or kinetic. Thermodynamics But on the microscopic scale it is a seething mass of high speed molecules traveling at hundreds of meters per second. If the water were tossed across the room, this microscopic energy would not necessarily be changed when we superimpose an ordered large scale motion on the water as a whole.  First Law of Thermodynamics Suppose 40.00 J of energy is transferred by heat to a system, while the system does 10.00 J of work. Later, heat transfers 25.00 J out of the system, while 4.00 J is done CONTENTS by work on the system. What is the net change in the system’s internal energy? Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics What is the change in the internal energy of a system when a total of 150.00 J is transferred by heat from the system and 159.00 J is done by work on the system? CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics How much work is done by a gas under 20 Pa of pressure increasing in volume by 3.0 m3 CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics What is the net heat out of the system when 25J is transferred by heat into the system and 45J is transferred out of it? CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics A gas in a closed container is heated, causing the lid of the container to rise. The gas performs 3J of work to raise the lid, such that is has a final total energy of 15J. How CONTENTS much heat energy was added to the system? Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics A gas in a closed container is heated with 50J of energy, causing the lid of the container to rise. If the change in energy of the system is 30J, how much work was CONTENTS done by the system? Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Types of Thermodynamic Systems CONTENTS There are three types of thermodynamic systems depending on the nature of the boundary. Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Isolated system: Third Law of A system which can exchange neither matter nor energy Thermodynamics with its surroundings is called an isolated system. Here boundary is sealed and insulated. Hot water contained in a thermos flask, is an example for an isolated system. In this isolated system both energy (heat) and matter (water vapour) neither enter nor leave the system.  First Law of Thermodynamics Closed system: A system which can exchange only energy but not matter with its CONTENTS surroundings is called a closed system. Here the boundary is sealed Zeroth Law of but not insulated. Hot water contained in a closed beaker is an Thermodynamics example for a closed system. In this system energy (heat) is transferred to the surroundings but no matter (water vapour) can First Law of escape from this system. A gas contained in a cylinder fitted with a Thermodynamics piston constitutes a closed system. Second Law of Open system: Thermodynamics A System which can exchange both matter and energy with its Third Law of surrounding is called an open system. Hot water contained in an open beaker is an example for open system. In this system both Thermodynamics matter (water vapour) and energy (heat) is transferred to the surrounding. All living things and chemical reactions are open systems because they exchange matter and energy with the surroundings.  First Law of Thermodynamics Closed system: A system which can exchange only energy but not matter with its CONTENTS surroundings is called a closed system. Here the boundary is sealed Zeroth Law of but not insulated. Hot water contained in a closed beaker is an Thermodynamics example for a closed system. In this system energy (heat) is transferred to the surroundings but no matter (water vapour) can First Law of escape from this system. A gas contained in a cylinder fitted with a Thermodynamics piston constitutes a closed system. Second Law of Open system: Thermodynamics A System which can exchange both matter and energy with its Third Law of surrounding is called an open system. Hot water contained in an open beaker is an example for open system. In this system both Thermodynamics matter (water vapour) and energy (heat) is transferred to the surrounding. All living things and chemical reactions are open systems because they exchange matter and energy with the surroundings.  First Law of Thermodynamics Types of Thermodynamic Conditions CONTENTS Free Expansion Zeroth Law of Isochoric Condition Thermodynamics First Law of Isobaric Condition Thermodynamics Isothermal Condition Second Law of Adiabatic Reversible Condition Thermodynamics Adiabatic Irreversible Condition Third Law of Thermodynamics  First Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Adiabatic Changes CONTENTS For Adiabatic Changes, ΔQ = 0 Zeroth Law of Thermodynamics ΔU = W First Law of In adiabatic changes, we can expect the temperature Thermodynamics to change Second Law of Thermodynamics Adiabatic changes can be expressed in terms of two Third Law of steps: Thermodynamics 1. the change in volume at constant temperature, 2. followed by a change in temperature at constant volume.  First Law of Thermodynamics Adiabatic Changes CONTENTS The overall change in internal energy of the gas only Zeroth Law of depends on the second step since internal energy is Thermodynamics dependent on the temperature. First Law of Thermodynamics ΔUad = wad = nCvΔT for irreversible conditions Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics How to relate P, V, and T? during adiabatic changes? CONTENTS Use the following equations: Zeroth Law of ViTic = VfTfc Thermodynamics Where c = Cv/R First Law of Thermodynamics PiViγ = PfVfγ Second Law of Where γ = Cp/Cv Thermodynamics Third Law of 𝑛𝑅∆𝑇 Thermodynamics Wad,rev = 1−γ  First Law of Thermodynamics Heat capacities are crucial thermodynamic CONTENTS properties that describe how much heat a Zeroth Law of substance can store. There are two primary types of Thermodynamics heat capacities: Cp​ and Cv. First Law of Cp​ (Heat Capacity at Constant Pressure) Thermodynamics It is the amount of heat required to raise the Second Law of temperature of a substance by one degree Celsius (or one Kelvin) while maintaining constant pressure. Thermodynamics Third Law of Cv (Heat Capacity at Constant Volume) Thermodynamics It is the amount of heat required to raise the temperature of a substance by one degree Celsius (or one Kelvin) while maintaining constant volume. Cp = Cv + R  First Law of Thermodynamics Other Notable Thermodynamic Relationships CONTENTS Cp = 5/2 R - Monoatomic gass Zeroth Law of Cv = 3/2 R - Monoatomic gas Thermodynamics First Law of cp = 7/2 R - diatomic gas Thermodynamics Cv = 5/2 R - diatomic gas Second Law of Thermodynamics Cp = 9/2 R - Triatomic gas Third Law of Cv = 7/2 R - Triatomic gas Thermodynamics For ideal gas: Cp - Cv = nR H - U = nRT  First Law of Thermodynamics Free Isothermal Isochoric Isobaric Adiabatic expansion CONTENTS Zeroth Law of ΔU 0 0 nCvΔT q+w w Thermodynamics First Law of nRT ln 𝑓 𝑉 nCpΔT or – q 0 𝑉𝑖 nCvΔT 0 Thermodynamics or -wirrev wirrev Second Law of 𝑉𝑓 𝑉𝑓 𝑛𝑅∆𝑇 Thermodynamics wrev 0 -nRT ln 0 -nRT ln 𝑉𝑖 𝑉𝑖 1−γ Third Law of Thermodynamics 𝑉 =-nCvΔT wirrev 0 -pextΔV 0 -‫𝑝 𝑓 𝑉׬‬d𝑉 𝑖 =-pextΔV 0 (for ideal =ΔU + pΔV =ΔU + pΔV ΔH 0 gas) =nCvΔT =nCpΔT  First Law of Thermodynamics 10 g of N2 is obtained at 17°C under 2 atm. Calculate ΔU, q, and w for the following processes of this gas, assuming it behaves ideally CONTENTS a) Reversible expansion to 10 L under 2 atm Zeroth Law of b) Adiabatic free expansion Thermodynamics c) Isothermal, reversible, compression to 2 L First Law of d) Isobaric, isothermal, irreversible expansion to 0.015 m3 under 2 atm e) Isothermal free expansion Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics 2 moles of a certain ideal gas is allowed to expand adiabatically and reversibly to 5 atm pressure from an initial state of 20°C and 15 atm. What will be the final CONTENTS temperature and volume of the gas? What is the change in internal energy during this process? Assume a Cp of 8.58 cal/mole K Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics 2 moles of a certain ideal gas is allowed to expand adiabatically and reversibly to 5 atm pressure from an initial state of 20°C and 15 atm. What will be the final CONTENTS temperature and volume of the gas? What is the change in internal energy during this process? Assume a Cp of 8.58 cal/mole K Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics 1 mole of an ideal gas at 300 K expands quasi-statically from 10 L to 20 L. Calculate the work done by the gas. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics If the molar heat capacity at constant volume (𝐶𝑣) for an ideal gas is 20.8 J/mol K, calculate the molar heat capacity at constant pressure (𝐶𝑝) CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the amount of heat required to raise the temperature of 2 moles of an ideal gas from 300 K to 400 K at constant volume if 𝐶𝑣=20.8 J/mol K CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the amount of heat required to raise the temperature of 3 moles of an ideal gas from 250 K to 350 K at constant pressure if 𝐶𝑝=29.114 J/mol K. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Second Law of Thermodynamics Thermodynamics Third Law of Thermodynamics  Second Law of Thermodynamics The Second Law of Thermodynamics is a CONTENTS fundamental principle that deals with the direction Zeroth Law of of spontaneous processes and the efficiency of Thermodynamics thermal engines. First Law of No process is possible in which the sole result is the Thermodynamics Second Law of absorption of heat from a reservoir and its complete Thermodynamics conversion into work Third Law of It states that the total entropy of an isolated system Thermodynamics can never decrease over time, and is constant if and only if all processes are reversible. This implies that natural processes tend to move towards a state of maximum entropy.  Second Law of Thermodynamics Entropy (𝑆): A measure of the disorder or CONTENTS randomness in a system. Higher entropy means Zeroth Law of more disorder and less energy available for doing Thermodynamics work. First Law of Spontaneous Processes: Processes that occur Thermodynamics naturally without external influence. According to Second Law of the Second Law, these processes always increase Thermodynamics the total entropy of the system and its Third Law of surroundings. Thermodynamics Reversible Processes: Idealized processes that can be reversed without leaving any net change in the system and surroundings. They are hypothetical and do not occur in reality but are useful for theoretical purposes.  Second Law of Thermodynamics Importance of the Second Law of Thermodynamics in CONTENTS Pharmacy Zeroth Law of Drug Stability: Understanding entropy changes helps in Thermodynamics predicting the stability of drugs under different First Law of conditions. Drugs are more stable when their entropy change during storage is minimized. Thermodynamics Second Law of Formulation and Storage: The Second Law assists in Thermodynamics optimizing drug formulations and storage conditions by ensuring that processes that increase disorder (and thus Third Law of degrade the drug) are minimized. Thermodynamics Pharmaceutical Processes: Manufacturing processes, such as crystallization and lyophilization (freeze-drying), rely on entropy changes to achieve the desired product characteristics.  Second Law of Thermodynamics Spontaneity CONTENTS Spontaneous process are those that occur naturally. Zeroth Law of Hot body cools Thermodynamics A gas expands to fill the available volume First Law of Thermodynamics Second Law of A spontaneous direction of change is where the Thermodynamics direction of change does not require work to bring it Third Law of about. Thermodynamics  Second Law of Thermodynamics Spontaneity CONTENTS The reverse of a spontaneous process is a Zeroth Law of nonspontaneous process Thermodynamics Confining a gas in a smaller volume First Law of Cooling an already cool object Thermodynamics Second Law of Thermodynamics Nonspontaneous processes require energy in order Third Law of to realize them. Thermodynamics  Second Law of Thermodynamics CONTENTS Hot Zeroth Law of Reservoir Thermodynamics First Law of Thermodynamics Heat Engine Work Second Law of Thermodynamics Third Law of Cold Heat Reservoir Thermodynamics  Second Law of Thermodynamics The Second Law can be expressed in terms of the CONTENTS entropy: Zeroth Law of Thermodynamics First Law of The entropy of an isolated system increases over Thermodynamics the course of a spontaneous change: ΔStot > 0 Second Law of Thermodynamics Third Law of Where Stot is the total entropy of the system and its Thermodynamics surroundings.  Second Law of Thermodynamics A simple definition of entropy is that it is a measure CONTENTS of the energy dispersed in a process. Zeroth Law of For the thermodynamic definition, it is based on the Thermodynamics expression: First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  Second Law of Thermodynamics For a measurable change between two states, CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics In order to calculate the difference in entropy Third Law of between two states, we find a reversible pathway Thermodynamics between them and integrate the energy supplied as heat at each stage, divided by the temperature.  Second Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  Second Law of Thermodynamics S as a function of T and V, at constant P CONTENTS 𝑇𝑓 𝑉𝑓 Zeroth Law of Δ𝑆 = 𝑛𝐶𝑝 𝑙𝑛 + 𝑛𝑅 ln 𝑇𝑖 𝑉𝑖 Thermodynamics First Law of Thermodynamics S as a function of T and P, at constant V Second Law of 𝑇𝑓 𝑃𝑓 Δ𝑆 = 𝑛𝐶𝑣 𝑙𝑛 − 𝑛𝑅 ln Thermodynamics 𝑇𝑖 𝑃𝑖 Third Law of Thermodynamics  Second Law of Thermodynamics Phase Transition/Phase Change CONTENTS ΔtransH Zeroth Law of ΔtransS = Ttrans Thermodynamics First Law of Thermodynamics Trouton’s rule: An empirical observation about a Second Law of wide range of liquids providing approximately the Thermodynamics same standard entropy of vaporization, around 85 Third Law of J/mol K. Thermodynamics  Second Law of Thermodynamics Isothermal Isochoric Isobaric Adiabatic CONTENTS Zeroth Law of ΔU 0 nCvΔT q+w w Thermodynamics 𝑉 nRT ln 𝑓 First Law of q 𝑉𝑖 nCvΔT nCpΔT or –wirrev 0 or -wirrev Thermodynamics 𝑛𝑅∆𝑇 Second Law of wrev -nRT ln 𝑉𝑓 0 -nRT ln 𝑉𝑓 𝑉𝑖 𝑉𝑖 1−γ Thermodynamics Third Law of wirrev -pextΔV 0 -pextΔV =-nCvΔT =-pextΔV Thermodynamics =ΔU + pΔV ΔH 0 (for ideal gas) ΔU =nCpΔT 𝑉𝑓 𝑇 𝐶𝑣𝑑𝑇 𝑇 𝐶𝑝𝑑𝑇 ΔS = 𝑛𝑅 𝑙𝑛 =‫ 𝑇׬‬2 =‫ 𝑇׬‬2 0 𝑉𝑖 1 𝑇 1 𝑇  Second Law of Thermodynamics The Second Law can be expressed in terms of the CONTENTS entropy: Zeroth Law of Thermodynamics First Law of The entropy of an isolated system increases over Thermodynamics the course of a spontaneous change: ΔStot > 0 Second Law of Thermodynamics Third Law of Where Stot is the total entropy of the system and its Thermodynamics surroundings.  First Law of Thermodynamics Calculate the change in entropy when 2 moles of an ideal gas are heated from 300 K to 400 K at constant volume. Assume 𝐶𝑣=20.8 J/mol K. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the change in entropy when 1 mole of an ideal gas expands isothermally from 10 L to 20 L at 300 K. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the total entropy change when 1 mole of oxygen gas at 300 K and 1 mole of nitrogen gas at 300 K are mixed in a container. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the total entropy change when 1 kg of water at 80°C is mixed with 1 kg of water at 20°C. Assume the specific heat capacity of water is 4.18 kJ/kg K. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Third Law of Second Law of Thermodynamics Thermodynamics Third Law of Thermodynamics  Third Law of Thermodynamics The entropy of all perfect crystalline substances is zero CONTENTS at T = 0. This law implies that it is impossible to reach absolute zero in a Zeroth Law of finite number of steps. Thermodynamics At T = 0, all energy of thermal motion has been First Law of quenched, and in a perfect crystal all the atoms or ions Thermodynamics are in a regular, uniform array. Second Law of The localization of matter and the absence of thermal Thermodynamics motion suggest that such materials also have zero Third Law of entropy. Thermodynamics This conclusion is consistent with the molecular interpretation of entropy, because S = 0 if there is only one way of arranging the molecules and only one microstate is accessible (the ground state).  Third Law of Thermodynamics Nernst heat theorem CONTENTS The entropy change accompanying any physical or Zeroth Law of chemical transformation approaches zero as the Thermodynamics temperature approaches zero: ΔS → 0 as T → 0 First Law of provided all the substances involved are perfectly Thermodynamics Second Law of crystalline. Thermodynamics Third Law of Thermodynamics  Third Law of Thermodynamics Absolute Zero: The lowest possible temperature, 0 CONTENTS Kelvin (-273.15°C), where molecular motion ceases. Zeroth Law of Thermodynamics First Law of The Third Law of Thermodynamics can be Thermodynamics expressed mathematically as: Second Law of Thermodynamics 𝑙𝑖𝑚 𝑇→0 𝑆 𝑇 = 0 Third Law of Thermodynamics  Third Law of Thermodynamics Importance in Pharmacy CONTENTS Drug Purity and Crystallization: The Third Law helps Zeroth Law of in understanding the behavior of substances at very Thermodynamics low temperatures, which is crucial for purifying First Law of drugs through crystallization. Thermodynamics Stability and Shelf Life: Insights into low- Second Law of temperature properties of drugs can aid in Thermodynamics developing better storage conditions, ensuring long- Third Law of term stability and efficacy. Thermodynamics Cryopreservation: The principles of the Third Law are applied in the cryopreservation of biological samples, such as tissues and organs, which is important for research and medical treatments.  Third Law of Thermodynamics Entropy Change as Temperature Approaches Zero 𝑇 CONTENTS 𝐶(𝑇 ′ ) Zeroth Law of ΔS = න 𝑑𝑇′ Thermodynamics 𝑇′ 0 First Law of Residual entropy (𝑆𝑟) refers to the entropy present Thermodynamics Second Law of in a system at absolute zero due to positional Thermodynamics disorder: Third Law of 𝑆𝑟 ​= kB​ ln Ω Thermodynamics Where: kB is Boltzmann's constant (1.38×10−23 J/K). Ω is the number of possible microstates.  First Law of Thermodynamics Calculate the entropy change of a perfect crystal of 1 mole as it is heated from 0 K to 10 K, given that the heat capacity C(T′)=aT′, where a is a constant 0.1J/mol K^2 CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the entropy change of a material with heat capacity 𝐶(𝑇′)=𝑏𝑇′^2, where 𝑏=0.05 J/mol K^3 , as it is heated from 0 K to 20 K. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the residual entropy of a crystal where each molecule can be in one of two positions. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the residual entropy of a system with four possible orientations for each molecule. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  First Law of Thermodynamics Calculate the residual entropy of a polymer chain with 𝑁N segments, each of which can be in one of three states. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Second Law of Thermodynamics Third Law of Thermodynamics  Summary Zeroth Law of Thermodynamics CONTENTS Statement: If two systems are each in thermal equilibrium with a third system, then they are in thermal equilibrium with each other. Zeroth Law of Implications: Thermodynamics This law allows the definition of temperature. It implies that temperature is First Law of a fundamental and measurable property of matter. In pharmacy, it ensures that thermometers can be used to measure the Thermodynamics temperature of substances accurately, which is crucial for maintaining the Second Law of stability and efficacy of drugs. Thermodynamics First Law of Thermodynamics Third Law of Statement: Energy cannot be created or destroyed, only transferred or Thermodynamics transformed. The total energy of an isolated system remains constant. Implications: This law is a statement of the conservation of energy. In pharmacy, it is essential for understanding and designing processes that involve energy changes, such as heating, cooling, and chemical reactions.  Summary Second Law of Thermodynamics CONTENTS Statement: The total entropy of an isolated system can never decrease over time. It can remain constant for a reversible process but increases for an Zeroth Law of irreversible process. Thermodynamics Implications: First Law of This law introduces the concept of entropy and dictates the direction of natural processes. Thermodynamics In pharmacy, it helps in understanding the stability of drugs, optimizing Second Law of manufacturing processes, and ensuring quality control. Thermodynamics Third Law of Thermodynamics Third Law of Statement: The entropy of a perfect crystal at absolute zero (0 Kelvin) is Thermodynamics exactly zero. Implications: This law provides a reference point for the measurement of entropy. In pharmacy, it is useful for understanding the behavior of substances at very low temperatures, important for drug crystallization and cryopreservation. CONTENTS Zeroth Law of Thermodynamics First Law of Thermodynamics Thank You! Second Law of Thermodynamics Third Law of Thermodynamics Physical Properties of Molecules and the Intramolecular and Intermolecular Forces of Attraction Ronnel C. Garcia, RChE, RChT, RPh CONTENTS Intramolecular Forces Intermolecular Forces CONTENTS Intramolecular Forces Intermolecular Forces Intramolecular Forces  Intramolecular Forces Intramolecular forces are the forces that hold atoms together within a molecule. These include covalent CONTENTS bonds, ionic bonds, and metallic bonds. Intramolecular Forces Covalent Bonds Intermolecular Forces Concept: Atoms share electron pairs to achieve a full outer electron shell. Lewis structures and VSEPR (Valence Shell Electron Pair Repulsion) theory help predict molecular shapes. Ionic Bonds Concept: Electrostatic attraction between positively charged cations and negatively charged anions. Born-Haber cycle can be used to calculate lattice energy. Metallic Bonds Concept: Attraction between free-floating valence electrons and positively charged metal ions. Electron sea model explains the properties of metals such as conductivity and malleability.  Intramolecular Forces Bond Energy (Covalent Bonding) CONTENTS Intramolecular Forces Intermolecular Forces E = D(A-B) E = bond energy D(A-B) = bond dissociation energy A-B represents the bonding of atom A and atom B  Intramolecular Forces Calculate the energy required to break all C−H bonds in a mole of methane if D(C−H)=414 kJ/mol CONTENTS Intramolecular Forces Intermolecular Forces  Intramolecular Forces Born-Haber cycle (Ionic Bonding) CONTENTS Used for calculation of Lattice Energy Intramolecular Forces 𝑘 (𝑞1 𝑥 𝑞2 ) Intermolecular Forces 𝑈= 𝑟 Where k is Coulomb's constant, Q1 and q2 are the charges of the ions, and r is the distance between them.  Intramolecular Forces Calculate the lattice energy of NaCl given r = 2.82 A˚ CONTENTS Intramolecular Forces Intermolecular Forces  Intramolecular Forces Calculate the lattice energy of MgO given r = 2.13 A˚ CONTENTS Intramolecular Forces Intermolecular Forces  Intramolecular Forces Calculate the lattice energy of CaF2 given 𝑟 = 2.31 A˚ CONTENTS Intramolecular Forces Intermolecular Forces CONTENTS Intramolecular Forces Intermolecular Forces Intermolecular Forces  Intermolecular Forces Intermolecular forces (IMFs) are the forces of attraction CONTENTS and repulsion between molecules that influence the physical properties of substances. These forces are Intramolecular Forces crucial in understanding the behavior of molecules in Intermolecular Forces different states of matter and are particularly important in fields such as pharmacy, where they affect drug formulation, stability, and bioavailability. This lecture covers the fundamental concepts, theories, and examples of various types of intermolecular forces. Types of Intermolecular Forces London Dispersion Forces (Van der Waals Forces) Dipole-Dipole Interactions Dipole-Induced Dipole Forces Hydrogen Bonds Ion-Dipole Interaction  Intermolecular Forces London Dispersion Forces (Van der Waals Forces) CONTENTS London dispersion forces are the weakest intermolecular Intramolecular Forces forces and arise due to temporary fluctuations in electron distribution within atoms and molecules, creating temporary Intermolecular Forces dipoles that induce dipoles in neighboring molecules. These forces are present in all molecules, whether polar or nonpolar, and their strength increases with the number of electrons in a molecule (i.e., its size and molar mass). Examples: Larger noble gases have more electrons, leading to stronger London dispersion forces, thus requiring more energy to vaporize. Butane has a higher molar mass and more electrons than ethane, resulting in stronger dispersion forces and a higher boiling point. Pentane has more electrons and larger surface area, leading to stronger London dispersion forces compared to methane.  Intermolecular Forces CONTENTS Intramolecular Forces Intermolecular Forces  Intermolecular Forces Dipole-Dipole Interactions CONTENTS Dipole-dipole interactions occur between polar Intramolecular Forces molecules, where the positive end of one dipole is Intermolecular Forces attracted to the negative end of another dipole. These interactions are stronger than London dispersion forces and are significant in determining the properties of polar compounds. Examples: HCl is polar with dipole-dipole interactions, whereas Cl2 is nonpolar with only dispersion forces, leading to a lower boiling point. Acetone has a polar carbonyl group that can form dipole- dipole interactions with water molecules, enhancing solubility. Dimethyl ether has dipole-dipole interactions due to its polar C-O bond, while propane only has dispersion forces, resulting in a higher boiling point for dimethyl ether.  Intermolecular Forces CONTENTS Intramolecular Forces Intermolecular Forces  Intermolecular Forces Dipole-Induced Dipole Forces CONTENTS Dipole-induced dipole forces occur when a polar Intramolecular Forces molecule induces a dipole in a nearby nonpolar Intermolecular Forces molecule. These interactions are generally weaker than dipole- dipole interactions but stronger than London dispersion forces. Examples: Iodine is nonpolar, but the polarizable electrons can interact with the dipole-induced forces from CCl4 Water's dipole can induce a dipole in the nonpolar O2 molecule, allowing for slight solubility. The dipole in methanol induces a dipole in helium, creating weak interactions that allow some solubility.  Intermolecular Forces CONTENTS Intramolecular Forces Intermolecular Forces  Intermolecular Forces Hydrogen Bonds CONTENTS Hydrogen bonds are a special type of di