PHYSICAL PHARMACY

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PHYSICAL CHEMISTY – branch of chemistry concerned with

physical properties and structure of matter and with laws and
PHASE DIAGRAM
theories of physical and chemical changes
F
PHYSICAL PHARMACY – application of physical chemistry in B

pharmacy; study of physicochemical properties of substances

A
used in drug formulation E

High T – High P  point B – liquid

PRESSURE
D
I. FORCES OF ATTRACTION High T – Low P  point C – gas
Point D – Triple Point
A. INRAMOLECULAR – intra (within) the molecule Point E – Critical Point (minimum
 Ionic Bond – transfer of electrons; metal (electron donor) + temperature and pressure;
Critical Liquid (Point F)
non-metal (electron acceptor); (ex. Na: p+ = 11; e- = 11 -> p+ =
11; e- = 10  charge = +1) C

o PERIODIC TRENDS REPRESENTING BONDS

 Ionization Energy – energy required remove electron
(low M; high NM) TEMPERATURE
GAS STATE:
 Electronegativity – ability to attract electrons (low M;
 Kinetic Molecular Theory
high NM)
o Gases are composed of small particles called atoms; total
 Covalent Bonds – sharing of electrons; non-metal + non-
volume is negligible in relation to space where they are
metal; polarity – difference in electronegativity (symmetrical
confined
= non-polar)
o Particles do not attract one another but move with
o Polar – unequal sharing of electrons; dipole moment – (ex.
complete independence
H α+-Brα-)
o Particles exhibit continuous random motion owing to their
o Non Polar – equal sharing of electrons (ex. Br-Br)
kinetic energy
B. INTERMOLECULAR – inter (between) the molecules
o Gases exhibit perfect elasticity (no energy exchange)
 Van der Waals
o Dipole-Dipole  P + P; Keesom Forces; orientation effect
o Dipole-Induced Dipole  P + NP; Debye Forces; inductive II. GAS LAWS
effect  at standard temperature (Kelvin = oC + 273) and pressure
o Induced Dipole-Induced Dipole  NP + NP; London Forces; (1atm = 760mmHg or torr; 76cmHg; 1.01325x106 dynes/cm2;
dispersive effect 1.01325x105 Pa or N/m2; 01325 bar)
 Ion-Induced Dipole  ion + NP  Boyle’s Law – constant temperature; increase P = decrease V;
I2  NP (solubility – 1:2950) inversely related
I2 + NaI/KI (solubilizing agent)  I3 + I2 = increase solubility 1
𝑃 ∝
 Hydrogen Bond – hydrogen atom + electronegative atom (N, 𝑉
* density = increase altitude; decrease volume; P 1V1=P2V2
O, F)
 Charles’ Law – constant pressure; increase T = increase V
𝑇1 𝑉1 𝑇1 𝑇2
𝑇 ∝𝑉; = 𝑜𝑟 =
𝑇2 𝑉2 𝑉1 𝑉2
* H2O – 1.0g/mL  4oC
 Gay Lussac’s Law  constant volume
𝑃1 𝑇1 𝑃1 𝑃2
𝑃 ∝𝑇; = 𝑜𝑟 =
𝑃2 𝑇2 𝑇1 𝑇2
o
* 121 C – 15-20psi

PAGE 1 OF 7 © MANOR REVIEW CENTER NOTES (K.L)

 Avogadro’s Law III. MICROMERITICS
𝑉1 𝑛1 𝑉1 𝑉2
𝑉 ∝ 𝑛 (𝑚𝑜𝑙𝑒𝑠) ; = 𝑜𝑟 = - micro (small); meritics (measure) – study of small particles
𝑉2 𝑛2 𝑛1 𝑛2
 Combined Gas Law
𝑃1𝑉1 𝑃2𝑉2 A. PARTICLE SIZE
𝑇1
=
𝑇2  METHODS:
 Ideal Gas Law o Sieve Analysis – USP method (official method); utilizes a
𝑔 𝑃(𝑀𝑊) series of standard sieves calibrated by National Bureau of
𝑃𝑉 = 𝑛𝑅𝑇 → = Standards; involves size classification followed by weight
𝐿 𝑅𝑇
𝑔𝑅𝑇 determination of each fraction
𝑀𝑊 =
𝑃𝑉  Mesh Number/Size – number of square opening per
o P = pressure (atm) linear inch; increase mesh number = decrease particle
o V = volume (L) size
o n = moles (gram/MW) GIVEN: 100g
o R = universal gas constant (0.08205 L-atm/mole-Kelvin) Mesh Number Grams of powder that did not pass
o T = temperature (K) 20 15g
 Dalton’s Law of Partial Pressure 40 25g
𝑃𝑡 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯ 𝑃𝑛 60 10g
𝑆𝑦𝑠𝑡𝑒𝑚 = 𝐺𝑎𝑠 𝐴 + 𝐺𝑎𝑠 𝐵 80 35g
𝑃𝑡 = 𝑃𝐴 + 𝑃𝐵 CP 15g
𝑃𝐴 = 𝑋𝐴 (𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛) ∗ 𝑃𝑡 1. What percent of the powder is greater than mesh
𝑛𝐴 number 60? (did not pass  60)
𝑃𝐴 = (𝑃 )
𝑛𝐴 + 𝑛𝐵 𝑡 15𝑔 + 25𝑔 + 10𝑔 = 50𝑔
𝑛𝐵
𝑃𝐵 = (𝑃 ) 50
𝑛𝐴 + 𝑛𝐵 𝑡 𝑥 100 = 50%
100
 Clausius Clapeyron Equation – Absolute Temperature α P 2. What percent of the powder is less than mesh number
𝑃2 ∆𝐻𝑣 (𝑇2 − 𝑇1) 60? (did pass)
log ( ) =
𝑃1 2.303(𝑅𝑇1𝑇2) 35𝑔 + 15𝑔
o P = pressure (atm or mmHg) 𝑥 100 = 50%
100𝑔
o T = temperature (K) 3. What percent of the powder is less than mesh number
o R = universal gas constant (8.314 joules/n-K  SI unit or 40 but greater than 80? (did pass  40; did not pass
1.987 cal/n-K  non-SI unit)  80)
o ∆Hv = latent heat of vaporation 10𝑔 + 35𝑔
o Latent Heat – amount of energy needed to convert one 𝑥 100 = 45%
100𝑔
phase to another per mole of the compound (joules/mole) o Optical Microscopy – most accurate; microscope eyepiece
 ∆HF = latent heat of fusion (melting); solid ↔ liquid is fitted with a micrometer where the diameter can be
 ∆Hv = latent heat of vaporation (evaporation); liquid ↔ measured
gas  UNITS:
 ∆Hs = latent heat of sublimation; solid ↔ gas micrometer/micron (µm or µ) = 10-6 m, 10-4 cm, 10-3
mm
milimicron (mµ) = 10-9 m = 1 nanometer
 3 TYPES OF DIAMETER: for asymmetrical particle)
S L G Martin’s – bisect particle
Ferret’s – longest, tangeant
Projected Area of Circle – area  assumed to occupy
+ Heat diameter of particle
- Heat
 Raoult’s Law – vapor pressure lowering; Po1 (pure solvent) >
P1 (solution) + solute = lowered vapor pressure
o ∆𝑉𝑃 = 𝑃1𝑜 − 𝑃1
o ∆𝑉𝑃 = 𝑋𝑠𝑜𝑙𝑢𝑡𝑒 (𝑃1𝑜 )
o 𝑃1 = 𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑃1𝑜 ) A
B
C

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 o Stokes’ Law – sedimentation rate  TYPES OF POROSITY:
𝑑2 (𝜌𝑠 − 𝜌𝑜 )𝑔 o Intraparticular Porosity
𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 𝑉𝑔 − 𝑉𝑝
18𝜂
 Velocity = sedimentation rate 𝑉𝑔
 d = diameter o Interpartiicular Porosity
 Ps = density of suspensoid 𝑉𝑏 − 𝑉𝑔
 Po = density of medium 𝑉𝑏
 g = gravity o Total Porosity
 η = viscosity 𝑉𝑏 − 𝑉𝑝
 Andreason Apparatus 𝑉𝑏
𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑥 18𝜂
𝑑= √ (𝜌𝑠 − 𝜌0 )𝑔
D. FLUIDITY – angle of repose (θ)
o Automated Particle Canter  θ < 30o  free flowing; θ > 40o  + flow enhancer (glidant);
 Coulter Counter – electric resistance low height compared to spreadability = good flowing
 Hiac Rayco – light blockade characteristic
ℎ𝑒𝑖𝑔ℎ𝑡
𝑡𝑎𝑛𝜃 =
B. DENSITY 𝑟𝑎𝑑𝑖𝑢𝑠
𝑚𝑎𝑠𝑠
𝜌= E. COMPRESSIBILITY
𝑣𝑜𝑙𝑢𝑚𝑒
 Unit – g/mL (solid and liquid); g/L (gases)  Carr’s Index
 Absolute Density – determined in vacuum 𝑉𝑜 − 𝑉𝑓
𝐶𝑎𝑟𝑟 ′ 𝑠 𝐼𝑛𝑑𝑒𝑥 = 𝑥 100
 Apparent Density – determined in air 𝑉𝑜
 Specific Gravity – higher spg = at the bottom 0 = Vo = Vf NOT COMPRESSIBLE
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 1-99 = Vo > Vf COMPRESSIBLE
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑔𝑟𝑎𝑣𝑖𝑡𝑦 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑒𝑞𝑢𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 100 = Vf = 0 NOT POSSIBLE
𝜌𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒  Hausner’s Ratio
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑔𝑟𝑎𝑣𝑖𝑡𝑦 =
𝜌𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑𝑠 𝑉𝑜
 STANDARDS: 𝐻𝑎𝑢𝑠𝑛𝑒𝑟 ′ 𝑠 𝑅𝑎𝑡𝑖𝑜 =
𝑉𝑓
o Solid and Liquid – H2O 1 = Vo = Vf NOT COMPRESSIBLE
o Gas – air or hydrogen >1 = Vo > Vf COMPRESSIBLE
o Temperature – 25oC; alcohol – 15.56oC <1 = Vo < Vf NOT POSSIBLE
o Methods:
 Solid
IV. POLYMORPHISM AND HYDRATES
Hydrostatic Balance Method
Pycnometer Method/Specific Gravity Bottle Method  Cocoa Butter – suppository base
Graduated Cylinder Method o α – 22oC
Immersion of Solid in Transparent Liquid of Same o β – 34.5oC
Density o β’ – 28oC
 Liquids o ȣ - 18oC
Pycnometer Method – leach pycnometer   Insulin
thermometer o Short Acting – 100% amorphous
Floatation Method o Intermediate – 30% amorphous : 70% crystalline
- Hydrometer o Long Acting – 100% crystalline
- Mohr-Westphal Balance  Hydrates – contain water of crystallization
Monometrick Method – Fischer Davidson  Solubility – HYDROUS < ANHYDROUS
Gravitometer
LIQUID STATE
C. POROSITY – percent voids  Critical Temperature – temperature above which a liquid can
 TYPES OF VOLUME: no longer exist
o True Volume (Vp) – volume of particle without spaces  Critical Pressure – pressure required to liquefy gas at its
o Granular Volume (Vg) critical temperature
𝑉𝑔 = 𝑉𝑝 + 𝑖𝑛𝑡𝑟𝑎𝑝𝑎𝑟𝑡𝑖𝑐𝑢𝑙𝑎𝑟 𝑠𝑝𝑎𝑐𝑒  Boiling Point – temperature at which vapour pressure of
o Bulk Volume (Vb) liquid equals atmospheric pressure
𝑉𝑏 = 𝑉𝑝 + 𝑖𝑛𝑡𝑟𝑎𝑝𝑎𝑟𝑡𝑖𝑐𝑢𝑙𝑎𝑟 𝑠𝑝𝑎𝑐𝑒 + 𝑖𝑛𝑡𝑒𝑟𝑝𝑎𝑟𝑡𝑖𝑐𝑢𝑙𝑎𝑟 𝑠𝑝𝑎𝑐𝑒
𝑉𝑏 = 𝑉𝑔 + 𝑖𝑛𝑡𝑒𝑟𝑝𝑎𝑟𝑡𝑖𝑐𝑢𝑙𝑎𝑟 𝑠𝑝𝑎𝑐𝑒𝑠
PAGE 3 OF 7 © MANOR REVIEW CENTER NOTES (K.L)
SOLID STATE 3. Entropy (natural tendency of a process to occur) is zero at
 Crystalline Solid – solid whose structural units are arranged absolute zero
in fixed geometric patter; have definite melting point; have
definite shape and widely arrangement of units V. SOLUBILITY AND Ksp
 DISTINCT CRYSTALS BASED ON SYMMETRY  Solubility
o Cubic – NaCl 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑔)
o Tetragonal – urea 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑚𝐿 𝑜𝑟 𝐿)
o Rhombic – iodine  Molar Solubility (s)
o Hexagonal – iodoform 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑚𝑜𝑙𝑒𝑠)
o Monoclinic – sucrose 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑚𝐿 𝑜𝑟 𝐿)
o Triclinic – H3BO3
 Solubility Product Constant (Ksp) – product of molar solubility
of each component raised to an exponent equal to its
POLYMORPHISM – ability to exist in more than one crystalline stoichiometric coefficient
form; different melting point, x-ray crystal and diffraction o Capital-element  small coefficient
pattern 𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
 Enantiotropic – change is reversible 𝐾𝑠𝑝 = [𝐶 𝑠]𝑐 [𝐷 𝑠]𝐷
 Monotropic – change is irreversible o 2 SPECIES
 Amorphous Solids – supercooled liquids; arranged in random 𝑁𝑎𝐶𝑙 → 𝑁𝑎+ + 𝐶𝑙−
manner; no definite melting poing 𝐾𝑠𝑝 = [1 𝑠]1 [1 𝑠]1
o + cubic  isotropic – similar in all directions 𝐾𝑠𝑝 = 1𝑠1 1𝑠1
o + others  anisotropic – similar in one direction 𝐾𝑠𝑝 = 1𝑠 2
 Le Chatelier’s Principle – system at equilibrium readjust so as
𝑆 = √𝐾𝑠𝑝
to reduce effect of extended stress
o 3 SPECIES
o Concentration – forward and backward reactions;
𝐵𝑎𝐶𝑙2 → 𝐵𝑎+2 + 2𝐶𝑙−
reactions go towards less concentration
𝐾𝑠𝑝 = [1 𝑠]1 [2 𝑠]−2
o Pressure – favors side where there is least number of gas
𝐾𝑠𝑝 = 1𝑠1 4𝑠 2
mole
𝐾𝑠𝑝 = 4𝑠 3
o Temperature – endothermic (R + ∆  P; increase temp =
forward; decrease temp = backward) and exothermic 3 𝐾
𝑠𝑝
reactions (R  P + ∆; increase temp = backward; decrease 𝑆= √
4
temp = forward)
o 4 SPECIES
o Catalyst – no effect 𝐴𝑙𝐶𝑙3 → 𝐴𝑙+3 + 3𝐶𝑙−
𝐾𝑠𝑝 = [1 𝑠]1 [3 𝑠]3
MESOPHASE – liquid crystals; between solid and liquids
𝐾𝑠𝑝 = 1𝑠1 27𝑠 3
 Thermotropic – heating of solids
𝐾𝑠𝑝 = 27𝑠 4
 Lyotropic – action of solvent to solids
4 𝐾
 TYPES: 𝑠𝑝
𝑆= √
o Sinectic – soaplike or grease like; 2 direction 27
o Nematic – threadlike; 3 direction
 Cholesteric – special type
VI. COLLIGATIVE PROPERTIES
 Cholesteryl benzoate – first synthesized liquid crystal
 dependent on the numerical concentration than the nature
THERMODYNAMICS – deals with quantitative relationship of  Osmotic Pressure – pressure that resist osmosis
interconversion of various forms of energy o Osmosis – movement of water from high concentration
solvent to a lower concentration solvent through a semi-
 TYPES OF SYSTEMS:
permeable membrane; movement of water from low
o Open – energy and matter exchange
solute to high solute concentration through a semi-
o Closed – energy exchanged
permeable membrane
o Isolated – no exchange
o Van’t Hoff Equation
 LAWS:
 Non-Electrolytes: 𝜋 = 𝑀𝑅𝑇
1. Law of Conservation of Energy – energy can be
 Electrolytes: 𝜋 = 𝜄𝑀𝑅𝑇
transformed but cannot be created nor destroyed
2. Refers to probability of occurrence of process based on
tendency of a system to approach a state of energy
PAGE 4 OF 7 © MANOR REVIEW CENTER NOTES (K.L)
 Vapour Pressure Lowering – + solute = lower VP 3. Step 1 – Step 2
o Raoult’s Law 4. ** Step 3 / Evalue
∆𝑉𝑃 = 𝑃1𝑜 − 𝑃1 o Class II – addition of solvent; hypertonic  isotonic
∆𝑉𝑃 = 𝑋𝑠𝑜𝑙𝑢𝑡𝑒 (𝑃1𝑜 )  White Vincent Method – addition of water to make
𝑃1 = 𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑃1𝑜 ) solution isotonic, followed by addition of isotonic or
 Boiling Point Elevation – + solute = increase Tb isotonic-buffered solution to make solution to its final
Δ𝑇𝑏 = 𝑇𝑏𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 𝑇𝑏 𝑜 volume
𝛥𝑇𝑏 = 𝑚𝐾𝑏 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻2 𝑂 = 𝑤𝑡𝑑𝑟𝑢𝑔 𝑥 𝐸𝑣𝑎𝑙𝑢𝑒 𝑥 111.1
o Kb – Ebulloscopic Constant = 0.52oC/molal  Sprowl’s Method – simplification of white Vincent
o m – molality method wherein amount of drug is fixed at 1% of a
 Freezing Point Depression – + solute = lowering Tf fluidounce solution
Δ𝑇𝑓 = 𝑇𝑓 𝑜 − 𝑇𝑓𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻2𝑂 = 0.3𝑔 𝑋 𝐸𝑣𝑎𝑙𝑢𝑒 𝑥 111.1
𝛥𝑇𝑓 = 𝑚𝐾𝑓
o Kf – Cryoscopic Constant = 1.86oC/molal
VIII. pH AND BUFFER
o m – molality
 Strong Acid/Base
𝑝𝐻 𝑜𝑟 𝑝𝑂𝐻 = − log[𝐻 + 𝑜𝑟 𝑂𝐻 − ]
VII. ISOTONICITY [𝐻 + 𝑜𝑟 𝑂𝐻 − ] = 10−[𝑝𝐻 𝑜𝑟 𝑝𝑂𝐻]
 for parenteral/ophthalmic 𝑝𝐻 + 𝑝𝑂𝐻 = 14
 Isotonic Solution – same salt concentration to that of body  Weak Acid/Base
fluids o Weak Acid – acid constant (Ka)
 Hypotonic Solution – lower salt concentration compared to 𝑝𝐾𝑎 = − log[𝐾𝑎]
body fluids; swelling  burst o Weak Base – basic constant (Kb)
 Hypertonic Solution – higher salt concentration compared to 𝑝𝐾𝑏 = −log[𝐾𝑏]
body fluids; shrink  crenate 𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 14
 METHODS:  Henderson Hasselbalch Equation
o Class I – addition of solute; hypotonic  isotonic o Weak Acid
 D Method – Freezing Point Depression Method 𝑆𝑎𝑙𝑡
𝑝𝐻 = 𝑝𝐾𝑎 + log ( )
(Cryoscopic Method); blood = -0.52oC; 1 molal = -1.86oC 𝑊𝐴
𝑀𝑊 𝑠𝑎𝑙𝑡
𝑝𝐻 = (14 − 𝑝𝐾𝑏) + log ( )
10 = % 𝑎𝑐𝑖𝑑
1.86(𝜄) 0.52 𝑎𝑐𝑖𝑑
𝑝𝐻 = 𝑝𝑘𝑎 − log ( )
Strong Electrolytes – 100% dissolution; strong 𝑠𝑎𝑙𝑡
acids/strong bases; ɩ = 2 o Weak Base
Weak Electrolytes – incomplete dissociation (80%); 𝑊𝐵
𝑝𝐻 = 𝑝𝐾𝑎 + log ( )
weak acids/weak bases 𝑆𝑎
NUMBER OF IONS ɩ (80%)  Buffers – resist change in pH; weak acid + conjugate base;
2 1.8 weak base + conjugate acid
3 2.6 o Buffer Capacity/Index/Value/Efficiency  Van Slyke
4 3.4 Equation
5 4.2 𝐸𝑞
Δ𝑁 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝐿
 Non Electrolytes – do not dissociate; ɩ = 1 →
Δ𝑝𝐻 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑝𝐻
STEPS: o PREDOMINATION:
1. -0.52oC : 0.9% = D [Tf Drug] : x%  pH < pKa  unionized
2. 0.9% - Step 1  pH > pKa  ionized
3. Step 2 x volume of preparation  pH = pKa  maximum buffer capacity
 E Method – NaCl Equivalency Method
𝑔𝑟𝑎𝑚 𝑁𝑎𝐶𝑙
𝐸𝑣𝑎𝑙𝑢𝑒 =
1 𝑔𝑟𝑎𝑚 𝑑𝑟𝑢𝑔
𝑀𝑊𝑁𝑎𝐶𝑙 𝜄𝑑𝑟𝑢𝑔
𝐸𝑣𝑎𝑙𝑢𝑒 = 𝑥
𝜄𝑁𝑎𝐶𝑙 𝑀𝑊𝑑𝑟𝑢𝑔
STEPS:
0.9𝑔 𝑁𝑎𝐶𝑙
1. 0.9% NaCl  𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝𝑟𝑒𝑝
100𝑚𝐿
2. g drug x Evalue
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IX. REACTION KINETICS  CLASSIFICATION OF LIQUID ACCORING TO THE TYPE OF FLOW
o Newtonian Flow = F α G (ex. water acetone)
 moles disappearing; moles appearing
ZERO FIRST SECOND
K (rate 𝐶𝑜 − 𝐶𝑡 𝐶𝑜 1 𝐶𝑜 − 𝐶𝑡 1
ln ( ) ( ) ( )
constant) 𝑡 𝐶𝑡 𝑡 𝐶𝑜 𝐶𝑡 𝑡
t½ 0.5𝐶𝑜 0.693/𝐾1 1/𝐶𝑜 𝐾2
𝐾0 G η
T90 0.1𝐶𝑜 0.105/𝐾1 ---
𝐾0
Unit of K 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 1 1
𝑡𝑖𝑚𝑒 𝑡𝑖𝑚𝑒 𝑐𝑜𝑛𝑐. 𝑡𝑖𝑚𝑒
 Zero Order – constant rate of reaction; independent on F G
amount remaining; suspension; long term stability o Non-Newtonian Flow – non-time; shear dependent
𝐾𝒐 = 𝐾1 𝑥 𝑎𝑚𝑜𝑢𝑛𝑡 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑  Plastic Flow – Bingham Bodies
 First Order – constant fraction; dependent on amount of drug - associated with flocculated particles
remaining; solution; accelerated stability - presence of yield value (f)
𝐶𝑡 = 𝐶𝑜 𝑒 −𝐾𝑡 - Yield Value (f) – stress at which flow begins
 t ½ - Half Life – time wherein 50% is degraded and 50% - (ex. ointments, pastes, creams, cataplasm ceratesm
remained butter, margarine)
 t90 – Shelf Life – time wherein 10% of the drug is degraded
while 90% ( USP) remained
 Expiration Date
𝐸𝑥𝑝𝑖𝑟𝑎𝑡𝑖𝑜𝑛 𝐷𝑎𝑡𝑒 = 𝑀𝑎𝑛𝑢𝑓 𝐷𝑎𝑡𝑒 + 𝑡90 0f

G η
X. RHEOLOGY
 study of flow; branch of physics which deals with deformation
and flow of matter
 Absolute Viscosity (η) – internal friction; resistance of a fluid
to flow; Unit: poise (ρ) or dynes-s/cm2 0 f F G
 Kinematic Viscosity – Unit: stokes
𝑎𝑏𝑜𝑠𝑙𝑢𝑡𝑒 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦  Pseudoplastic Flow – shear thinning behavior; (ex. gums,
𝐾𝑖𝑛𝑒𝑚𝑎𝑡𝑖𝑐 𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 = tragacanth, Na alginate, methyl cellulose); exhibited by
𝑑𝑒𝑛𝑠𝑖𝑡𝑦
polymer in solution
 Relative Viscosity – no unit
𝐹 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 ↓𝜂=
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 = 𝐺 ↑
𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 𝐻2 𝑂
 FACTORS AFFECTING VISCOSITY
o Gas – ↑ temp, ↑ η
o Liquids
 ↑ temp, ↓ η
 ↓ MW, ↓ η
 + electrolytes, ↓ η G η
 + organic substance, ↑ η
 Newton’s Law of Flow – the higher the viscosity of liquid, the
greater the shearing stress is required to produce a certain
rate of shear
𝐹 (𝑠ℎ𝑒𝑒𝑟 𝑠𝑡𝑟𝑒𝑠𝑠) F G
𝜂=
𝐺

PAGE 6 OF 7 © MANOR REVIEW CENTER NOTES (K.L)

  Dilatant Flow – shear thickening behavior; associated
with particles which do not tend to aggregate or stick
together; (ex. paint suspension: >50%)
𝐹↑
↑𝜂=
𝐺 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑠𝑙𝑜𝑤)

G η

F G
o Non-Newtonian – time dependent
 Thixotropy – reversible gel-sol; (ex. SiO2, Mg Bentonite,
Na Bentonite); through time: ↓η (due to hysteresis) –
pseudoplastic
 Theopexy – start as pseudoplastic; through time ↑η; (ex.
Gypsum paste; synovial fluid)
 INSTRUMENTS:
o Single Point Viscometer
 Capillary Viscometer – Ostwald Saybolt
Poiseulle’s Method:
𝑟 5 𝜌𝑡𝜋
𝜂=
8𝑣𝑙
 r – radius (cm)
 ρ – density (g/cm3)
 t – time to flow (s)
 v – volume – cm3
 l – length – cm
 Falling Sphere Visco – Hoppler Visco
o Multipoint Viscometer
 Cup and Bob Viscometer
Searle Type – bob is rotating
- Stormer; Haake – rotovisko; Brookfield; Synchro-
electric viscometer
Cone and Plate – Ferranti-Shirley Viscometer
o Others: Penetrometers – ointment  viscoelasticity

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