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States of matter

  1. 1. STATES OF MATTER Presented by (Dr) Kahnu Charan Panigrahi Asst. Professor, Research Scholar, Roland Institute of Pharmaceutical Sciences, (Affiliated to BPUT) Web of Science Researcher ID: AAK-3095-2020
  2. 2.  Gases are compressible fluids. Their molecules are widely separated.  Liquids are relatively incompressible fluids. Their molecules are more tightly packed.  Solids are nearly incompressible and rigid. Their molecules or ions are in close contact and do not move. Comparison of Gases, Liquids and Solids
  4. 4.  A crystalline solid possesses rigid and long-range specific order.  In a crystalline solid, atoms, molecules or ions occupy (predictable) positions.  An amorphous solid does not possess a well-defined arrangement and long-range molecular order. Solids and the crystalline state
  5. 5. According to the nature of bond classified to fallowing group: • Ionic Crystals • Covalent Crystals • Metallic Crystals • Molecular Types of Crystals
  6. 6. No. of crystal system = 7 No. of Space lattice = 14 No. of Geometric structure = 230 NaCl urea iodine sucrose Boric acid Crystal forms iodoform Thymol
  8. 8. • Polymorphism is the ability of a substance to exist in more than one crystal structure • When the change from one form to another is reversible, it is said to be enantiotropic. • When the transition takes place in one direction only—for example, from a metastable to a stable form—the change is said to be monotropic. • Element exist in two or more distinct crystalline species called as allotropy. • Form having high melting point and low solubility are stable form, while form having low melting point and high solubility called metastable form Polymorphism
  9. 9. Applications of Polymorphism  SOLUBILITY: Riboflavin form I < form II < form III  DISSOLUTION: Methylprednisolone form I < form II  Melting point of Coca butter: Theobroma oil can exist in 4 different polymorphic forms of which only one is Stabile 1. Unstable gamma form melting at 18°C 2. Alpha form melting at 22°C 3. Beta prime form melting at 28°C 4. Stable beta form melting at 34.5°C  If the oil is heated to a point where it is completely liquified (about 35 C), the crystals of the stable polymorph are destroyed & the mass does not crystallize until it is cooled to 15 C.  The crystals that form are unstable & the suppositories melt at 24 C. Theobroma suppositories must be prepared below 33 C.
  10. 10. Carbamazepine
  11. 11. PSEUDOMORPHISM • Pseudomorphs are defined as those solid which form inclusion of small amount of solvent. • In case of stoichimetric type of adduct, the solvent molecules are incorporated in the crystal lattice which are called as solvates and the solvent called as solvent of crystallisation. • When the solvent associated is water then solvate are called as hydrate. • Generally anhydrous form has grater water solubility than the hydrates • organic solvates have better aqueous solubility than anhydrous form. • The anhydrous form of ampicillin have higher aqueous solubility then hydrous form • Chloroform solvate of griseofluvin have more aqueous solubility than non- solvate form.
  12. 12. Amorphous Solid  An amorphous solid does not possess a well-defined arrangement and long- range molecular order.  Amorphous substances, as well as cubic crystal, are isotropic, that is, they exhibit similar properties in all direction.  In these solids particles are randomly arranged in three dimension.  They don’t have sharp melting points.  Amorphous solids are also known as super cooled liquid.  Amorphous solids melt over a wide range of temperature
  13. 13. • Increasing order of melting point AMORPHOUS < METASTBLE < STABLE • Increasing order of solubility STABLE < METASTBLE <AMORPHOUS • The crystalline from of novobiocin acid is poorly absorbed, where as the amorphous form is readily absorbed and therapeutically active.
  14. 14. Differential scanning calorimetry • PRINCIPLE: It is a technique in which the difference in heat required to increase temperature of the sample & reference material is measured as a function of temp. or time. • Endothermic reaction: if sample absorbs some amount of heat during phase transition then reaction is said to be endothermic. Downward peak result • E.g. Melting, boiling, sublimation, vaporization, de-solvation. 12/14/2021 K.C. PANIGRAHI 14
  15. 15. • Exothermic reaction: if sample released some amount of heat during phase transition, then reaction is said to be exothermic. Upward peak result. • E.g crystallization, degradation, polymerization • Glass Transition temp(Tg): Temp at which an amorphous polymer or an amorphous part of crystalline polymer goes from hard , brittle state to soft or rubbery state. 12/14/2021 K.C. PANIGRAHI 15
  16. 16. 12/14/2021 K.C. PANIGRAHI 16
  17. 17. Application of DSC • During pre-formulation, it is important to identify the polymorph that are stable • A sharp melting endotherm indicates the relative purity where as broad asymmetric curve suggest impurity. • DSC with the support of x-ray diffraction & infrared spectroscopy are used as screening technique for the compatibility testing of drug with excipient. • The disappearance of the DSC peak of the drug is the proof of complexation in solid state.
  18. 18. X-RAY POWDER DIFFRACTION PRINCIPLE: • X-RAY powder diffractometry is used to characterize spray dried, crystalline material & the binary mixtures. • x-ray are diffracted & order of this diffraction is measured in form of graph between spectra intensity vs 2ɵ (0-40) • Diffraction occurs as a result of the interaction of radiation with electron of atom. • Because x-rays have wavelengths of about the same magnitude as the distance between the atoms or molecules of crystal. 12/14/2021 K.C. PANIGRAHI 18
  19. 19. Application of X-ray diffraction • Structure of Crystals • Polymer Characterization • Identification Of Impurity • identify the solvated and anhydrous forms of a compound • XRD is widely used to determine the degree of crystallinity of pharmaceuticals Bragg’s law: When X ray is diffracted by the atom a relationship between wavelength, angle of incidence light and distance between successive atomic plane was established as: nƛ = 2d sin ɵ Where n = 1,2,3 … order of reflection This equation is applied to calculate distance between the plane. 12/14/2021 K.C. PANIGRAHI 19
  20. 20. XRD patterns of (a) crystalline and (b) amorphous sucrose 12/14/2021 K.C. PANIGRAHI 20 Degree of crystallinity 𝒙 = 𝑰𝒄 𝑰𝒄+ 𝑰𝒂 x 100
  21. 21. LIQUID STATE
  22. 22. General properties • Liquids are denser than gases and occupy a definitevolume and density due to the presence of van der Waalsforces unlike gases. • Liquid have no definite shape like gases • Liquids have translational motion i.e. liquids move as a whole • If we allow gas to expand rapidly (inside a vacuum flask) so that no heat enters system, such expansion is known as adiabatic expansion. • As a result of that temperature of gas reduces. This cooling effect is known as Joule- Thomson effect. • Inversion temperature is the temperature below which gas cool when expand. (H= -80C and He =-240C) • When the rate of condensation equals the rate of vaporization at a definite temperature, the vapour becomes saturated and a dynamic equilibrium is established. • The pressure of the saturated vapour above the liquid is then known as the equilibrium vapourpressure.
  23. 23. Vapor pressure of liquids Clausius–Clapeyron equation • Any point on one of the curve represents a condition in which the liquid and the vapor exist together in equilibrium. • If the temperature of any of the liquids is increased while the pressure is held constant, or if the pressure is decreased while the temperature is held constant, all the liquid will pass into the vapour state. • The area covering right side of curve represent vapour phase while on left side represent liquid phase.
  24. 24. Vapor pressure of liquids Clausius–Clapeyron equation Clausius–Clapeyron equation expresses the relationship between the vapor pressure and the absolute temperature of a liquid: log 𝑷𝟐 ∆𝑯𝒗 𝑻𝟐−𝑻𝟏 = 𝑷𝟏 2.303 𝑹𝑻𝟏𝑻𝟐 P1 and P2: vapor pressures at absolute temperatures T1 and T2. ΔHv: the molar heat of vaporization (the heat absorbed by 1 moleof liquid when it passes into the vapor state). For water it is 40.67MJ/kmol
  25. 25. Boiling point The temperature at which the vapor pressure of the liquid equals the external or atmospheric pressure isknown as the boiling point. The absorbed heat used to change the liquid to vapor (at constant temperature i.e., boiling point) is called the latent heats of vaporization. For water it is 40.67MJ/kmol
  26. 26. Boiling point • The temperature at which the vapor pressure of the liquid equals an atmospheric pressure of 1 atm is called normal boilingpoint • At higher elevations, the atmospheric pressure decreases and the boiling point is lowered. • At a pressure of 700 mm Hg, water boils at 97.7°C; at 17.5 mm Hg, it boils at 20°C. • The change in boiling point with pressure can be computed by using the Clausius–Clapeyron equation. • Polar molecules (e.g water) exhibit high boiling points and high heats of vaporization because they are associated through hydrogen bonds. • Alcohols boil at a much higher temperature than saturated hydrocarbons through hydrogen bonding. • The boiling points of carboxylic acids are higher than that of alcohols because the acids form dimers through hydrogen bonding.
  27. 27.  Critical temperature (Tc) is the temperature above which the gas cannot be made to liquefy, OR is the temperature above which the liquid can no longer exist  The critical pressure (Pc) is the minimum pressure required to liquefy a gas at its critical temperature.  Critical temperature (Tc) of water is 374°C, or 647 K, and its critical pressure (Pc) is 218 atm or 22.08 pa. • Critical temperature (Tc) of Carbon dioxide is 31.1°C, and its critical pressure (Pc) is 7.37 pa. Liquefaction of Gases
  28. 28. Supercritical fluid • When a compound is subjected to a pressure and a temperature higher than its critical point, the fluid is said to be " supercritical " . • In the supercritical region, the fluid exhibits particular proporties and has an intermediate behaviour between that of a liquid and a gas. • In particular, supercritical fluids (SCFs) possess liquid-like densities, gas-like viscosities and diffusivities intermediate to that of a liquid and a gas. And hence termed as mesophase. • The fluid is said "supercritical" when it is heated above its critical temperature and compressed above its critical pressure.
  29. 29. • Carbon dioxide (CO2) is the most widely used supercritical fluid. This is because CO2 is chemically inert, non-toxic, non- flammable and the critical point of CO2 is easily accessible. (critical temperature 31°C and critical pressure 74 bar). • Due to its interesting properties Supercritical CO2 can be described as a ‘green solvent’. • All supercritical fluids are completely miscible with each other • Application: food extraction, volatile oil extraction, chromatography, Elimination of toxic substance, Crystallisation of compound.
  30. 30. Liquid Crystal • Liquid crystals (LCs) are a state of matter which has properties between those of conventional liquids and those of solid crystals. For instance, a liquid crystal may flow like a liquid, but its molecules may be oriented in a crystal-like way hence posses refractive index.
  31. 31. • In a nematic phase ("thread-like") the molecules are aligned in the same direction but are free to drift around randomly, very much as in an ordinary liquid. • Owing to their polarity, the alignment of the rod-like molecules can be controlled by applying an electric field. • In smectic ("soap-like") phases the molecules are arranged in layers, with the long molecular axes approximately perpendicular to the laminar planes. T • The only long-range order extends along this axis, with the result that individual layers can slip over each other (hence the "soap-like" nature) in a manner similar to that observed in graphite. • Cholesteric liquid crystal is a combination of nematic and smectic type.
  33. 33. Ideal Gas Equation 1 Boyle’s law: P  V (at constant n and T) Charles’ law: V  T (at constant n and P) Avogadro’s law: V  n (at constant P and T) P1V T1 = P2V T 2 PV = nRT R is the gas constant 2 1 Combined Gas Equation GASEOUS STATE LAW
  34. 34. • Dalton’s Law: P = p1 + p2 + p3 + ……… • Grahm’s law: µ = √3RT/M
  35. 35.  The conditions 0 0C and 1 atm are called standard temperature and pressure (STP).  Experiments show that at STP, 1 mole of an ideal gas occupies 22.414 L. PV = nRT R = PV = nT (1 atm)(22.414L) (1 mol)(273.15 K) R =0.082057 L • atm / (mol • K)
  36. 36. 9 What is the volume (in liters) occupied by 49.8 g of HCl at STP? PV = nRT V = nRT P T = 0 0C = 273.15 K P = 1 atm n = 49.8 g x 1 mol HCl 36.45 g HCl = 1.37 mol V = 1 atm 1.37 mol x 0.0821 L•atm x 273.15 K mol•K V = 30.7 L 1 atm ≈760.001 mm-Hg
  37. 37. Phase Equilibria & The Phase Rule Gibbs phase rule stated as: A gaseous mixture of CO2 and N2:F = 2 - 1 + 2 = 3 Three variables: pressure, temperature and composition. This is a trivariant system.
  38. 38.  A phase is defined as any homogeneous and physically distinct part of a system which is separated from other parts of the system by interfaces.  A part of a system is homogeneous if it has identical physical properties and chemical composition throughout the part.  Liquid water, pieces of ice and water vapour are present together. The number of phases is 3 as each form is a separate phase.  Calcium carbonate undergoes thermal decomposition. The chemical reaction is: CaCO3(s) = CaO (s) + CO2 (g) Number of phases = 2 : This system consists of 2 solid phases, CaCO3 and CaO and one gaseous phase, that of CO2 Phase Definition
  39. 39.  The number of components of a system at equilibrium is the smallest number of independently varying chemical constituents using which the composition of each and every phase in the system can be expressed.  A mixture of ethanol and water is an example of a two component system. We need both ethanol and water to express its composition. Components Degrees of freedom  The degrees of freedom is the least number of intensive property which must be fixed in order to define the system completely. temperature pressure Concentration Density
  40. 40. 610.25 Pa Applications: Freeze Drying
  41. 41. The Critical Solution Temperature: CST  Is the maximum temperature at which the two conjugate solution merges into one layer in all proportion. (or upper consolute temperature).  In the case of the phenol-water system, this is 66.8oC (point h) at 34% phenol  All combinations of phenol and water > CST are completely miscible and yield 1- phase liquid systems.  Application: Purity of phenol
  43. 43.  A eutectic mixture is defined as a mixture of two or more components which usually do not interact to form a new chemical compound but, which at certain ratios, inhibit the crystallization process of one another resulting in a system having a lower melting point than either of the components  EMLA® (lidocaine 2.5% and prilocaine 2.5%) Cream  EMLA Cream (lidocaine 2.5% and prilocaine 2.5%) is an emulsion in which the oil phase is a eutectic mixture of lidocaine and prilocaine in a ratio of 1:1 by weight. This eutectic mixture has a melting point below room temperature at 18 C and therefore both local anesthetics exist as a liquid oil rather than as crystals Eutectic mixture : Pharmaceutical Application
  44. 44. THANK YOU