CHEM

intermolecular forces

forces of attraction between molecules

intramolecular forces

hold atoms together in a molecule

partial charge

a charge less than that of a proton or electron

condensed phases

solids and liquids

Polarizability

the ease with which the electron distribution in the atom or molecule can be distorted

Electronegativity

A measure of the ability of an atom in a chemical compound to attract electrons

Polar molecule

molecule with an unequal distribution of charge, resulting in the molecule having a positive end and a
negative end

nonpolar molecule

molecule that shares electrons equally and does not have oppositely charged ends

dipole moment

represented by arrows with the arrowhead pointing toward the more electronegative atom (with lone
pairs)

induced dipole forces

When an ion or a dipole induces a dipole in an atom or molecule with no dipole

Concentrations of Solution
Colligative properties depend on...

relative numbers of solvent and solute molecules (mole fraction)

Colligative properties include:

1) Vapor pressure lowering

2) Boiling point elevation
3) Freezing point depression
4) Osmotic pressure

Osmosis is the

solvent migration across a semipermeable membrane that allows the solvent (but NOT the solute)
molecules to pass through (measured as osmotic pressure)

Freezing point depression may be treated as

eutectic melting

deltaTf = Kfm2 = Kf x ((1000w2)/(w1M2))

Calculate the Kf for water (Tf = 273.2K, deltaHf = 1437 cal/mol, R = 1.987 calmol^-1K^-1, MW = 18.02).
Then, calculate the freezing point depression of a solution containing 50 g dextrose (MW = 180.2) in
1000 g of water.

Kf = (RTf^2/deltaHf) x (MW of solvent/1000 g)

Kf = ((1.987 cal*mol^-1K^-1 x (273.2K)^2)/1437 cal/mol) s (18.02 g water/mole/1000 g)

Kf = 1.86 K*kg/mol

deltaTf = Kfm

deltaTf = 1.86 K * kg/mol x 50 g dextrose/180.2 g/mole dextrose = -0.516 degrees C

Always report freezing point depression as a negative value

The addition of 50 g dextrose to 1 L of water will decrease the freezing point of the solution by 0.52
degrees C

For an ideal gas mixture, the total pressure of a gaseous mixture is equal to

the sum of the pressures of the constituent species (Dalton's Law)

Some solutions are considered

ideal solutions (ex: dilute solutions that contain non-volatile solute)

For an ideal solution (that contains 2 species) the total vapor pressure is linearly related to the

partial vapor pressure and the mole fraction of the constituents (Raoult's Law)

p1 = p1^o x X1
p2 = p2^o x X2
p = p1 + p2

p1 and p2 are the

partial pressures of the solvent and the solute, respectively

X1 and X2

are their respective mole fractions

p1^o and p2^o are the

vapor pressures of the pure solvents (no solute)

Ideal solution behavior can be expected for components that are similar in _____ and _________

size, intermolecular reactions

For non-ideal solutions, the pressure-composition diagram has either

minimum or maximum total vapor pressure curve

See slide 14 Colligative Properties Solutions

A dilute solution containing a nonvolatile solute may be considered as an ideal solution such that p2
goes to 0 (for the solute) and:

p = p1 = p1^o x X1

Since X1 + X2 = 1, and therefore X1 = (1 - X2) such that:

p = p1 = p1^o x X1 = p1^o x (1 - X2)

p1 - p1^o = delta(p1) = -p1^o x X2

Lowering of the vapor pressure for dilute solution depends only on

the mole fraction of the solute

delta(p1)/p1^o = - X2

Relative vapor pressure lowering of the solution is equal to the mole fraction of the solute

In terms of molality, the vapor pressure lowering delta(p1) can be re-written as a function of the
molal concentration of the solute as follows:

delta(p1) = - (m/(m + 55.5) x p1^o

Subscript 1 is for _____ and subscript 2 is for _______

solvent, solute

Calculate the vapor pressure lowering of a solution containing 50 g dextrose (MW = 180) in 1000 g of
water. The vapor pressure of water is 23.77 mmHg at 25 degrees C

1) Known: 50 g dextrose (MW = 180) dissolved in 1000 g of water at 25 degrees C. p1^o = 23.77 mmHg
2) Calculate the vapor-pressure lowering, delta p1
3) What should you know?
delta(p1) = - (m/(m + 55.5) x p1^o
4) To calculate delta(p1), you need to calculate m for dextrose

50 g dextrose x 1 mol dextrose/180 g dextrose = 0.278 mol/kg = m

delta(p1) = - (0.278 mol dextrose/(0.278 mol dextrose + 55.5 mol water)) x 23.77 mmHg = -0.12 mmHg

Calculate the vapor pressure depression of water in the presence of 0.155 M of NaCl at 20 degrees C?

The vapor pressure of pure water (p1^o) is 17.54 mmHg at 20 degrees C

delta(p1) = - p1^o x X2

1) NaCl dissociates completely into Na+ and Cl- ions in water. As a result, for each mole of NaCl, there
will be 2 moles of solute constituents.

2) molarity = 0.155 x 2 = 0.310 M

3) X2 = n2/(n1 + n2)
approximately = n2/n1 = M2/(density of solute/molecular weight of solute) =
(0.31 mol/L)/55.56 mol/L

4) delta(p1) = - p1^o x X2 = (17.54 mmHg) x ((0.31 mol/L)/55.56 mol/L) = 0.098 mmHg

Can a solid have a vapor pressure?

Yes, ex: ephedrine

Used as a stimulant and for treating hypertension asssociated with anesthesia

See slide 19 Colligative Properties Solutions

The change in the vapor pressure of the solid (Clausius-Clapeyron equation) occurs via the heat of
sublimation such that:
d(ln P)sub = (deltaHsub)/(RTf^2)x dTf

Tf is freezing point of pure solvent

The change of the vapor pressure for the solution consists of the lowering of the vapor pressure by

the solute addition and then the temperature change

d(ln P)solute = -dXb

d(ln P)temp = deltaHvap/(RTf^2) x dTf

At equilibrium:
d(ln P)sub = d(ln P)solute + d(lnP)temp

Vapor phase mediated redistribution of Drug in tablet

See slide 22 Colligative Properties Solutions

Nitroglycerin: a vasodilator to treat heart conditions, such as angina and chronic heart failure

To solve the problem, evaporation of nitroglycerin must be depressed by reducing its vapor pressure, by
mixing it with PEG 400

The vapor pressure of pure chlorfluorocarbon, CFC 11, (MW = 137.4) at 21 degrees C is P11^o = 13.4
lb/in^2 (psi) and that of CFC 12 (MW = 120.9) is P12 ^o = 84.9 psi.
1) What is the partial pressure of CFCs 11 and 12 in the 50:50 mixture?
2) What is the total vapor pressure of a 50:50 mixture by gram weight of the 2 propellants?

1) Pi = XiPi^o
P11 = 0.5 mole fraction x 13.4 psi = 6.7 psi
P12 = 0.5 mole fraction x 84.9 psi = 42.4 psi

2) Ptotal = P11 + P12 = 6.7 psi + 42.4 psi = 49.1 psi

The boiling point of a liquid is the temperature at which vapor pressure of liquid is equal to

the external (ex: atmospheric) pressure

delta(p1)/p^o = - X2

Addition of nonvolatile solution

See slide 25 Colligative Properties Solutions

1) lowers the vapor pressure of the pure solvent, and therefore,

2) the solution must be heated to higher temperatures to boil (boiling point elevation)

Clapeyron Equation
deltaTb = ((RTb^2)/deltaHv) x X2

delta Tb = elevation of boiling point

Raoult's law

deltaTb approximately = Kbm2

delta Tb = elevation of the boiling point

m2 = molality of solution
Kb = boiling point elevation constant

Kb is

different for different solvents

Boiling point elevation equations (Clapeyron Equation & Raoult's law)

remove the negative sign because vapor pressure of solution is increased at elevated temperature

Boiling point elevation is independent of all other properties of solute except

molar fraction in the solution = colligative property

As result, boiling point of solution is related to that of pure solvent as follows:

Tb(solution) = Tb(solvent) + deltaTb

Boiling temperature of water is 100 degrees C at 1 atm with latent heat of vaporization (deltaHv) of 9.72
kcal/mol. Calculate the boiling point elevation of water upon adding 0.155 M NaCl at 1 atm (R = 1.987
cal/mol x K)

Concentration of ions = 0.155 x 2 = 0.31 M

X2 approx = (0.31 mol/L)/55.5 mol/L

deltaTb = ((RTb^2)/deltaHvap) x X2

deltaTb = ((1.987 cal/(mol x K) x (100 + 273)^2 x K^2)/9720 cal/mol) x (0.31 mol/L)/55.5 mol/L = 0.159 K
= 0.159 degrees C

deltaTb approx = Kbm2

Kb = deltaTb/m2
= 0.159 degrees C/0.31 mol/kg
= 0.51 degrees C x kg/mole
Calculate the relative vapor pressure lowering at 20 degrees C for a solution containing 171.2 g sucrose
in 100 g water. The molecular weight of sucrose is 342.3 and the molecular weight of water is 18.02 g
(vapor pressure of water at 20 degrees C is 17.54 mmHg)

delta(p1) = - p1^o x X2

X2 = n2/(n2 + n1)
= 171.2 g/(342.3 g/mol)/((171.2 g/342.3 g/mol) + 100 g/18.02 g/mol)

X2 = 0.5/(0.5 +5.5) = 0.083

delta p1 = -17.54 mmHg x 0.083 = 1.46 mmHg

Vapor pressure is lowered by 1.46 mmHg

Calculate the vapor pressure when 0.5 mole of sucrose (n2) is added to 1000 g of water at 20 degrees C.
The vapor pressure of pure water is 17.54 mmHg.

delta p1 = - p1^o x X2

X2 = n2(n2 +n1) =
0.5 mol/(0.5 mol + 1000g/18.02 g/mol) =
approximately 0.5/55.5 =
0.009

delta p1 = -17.54 mmHg x 0.009 = -0.16 mmHg

Vapor pressure is lowered by 0.16 mmHg

A solution of sucrose (MW 342) is prepared by dissolving 0.5 g in 100 g of water. Compute a) weight
percent b) molal concentration and c) mole fraction of sucrose and water in solution

a) weight percent = 0.5 g sucrose/100.5 g solution x 100% = 0.498% (w/w)

b) molality = moles/kg solvent

0.5 g sucrose x 1 mole sucrose/342 g sucrose = 0.001462 moles sucrose
100 g water x 1 kg/1000g = 0.1 kg water
0.001462 moles sucrose/0.1 kg water = 0.01462 m sucrose

c) mole fraction = n1/(n1 + n2)

1 mole water = 18.01 g
100 g water x 1 mole water/18.01 g water = 5.55 mole water
0.01462 moles sucrose/(0.01462 moles sucrose + 5.55 moles water) = 0.0002629 mole fraction sucrose
5.55 moles water/(0.01462 moles sucrose + 5.55 moles water) = 0.999737 mole fraction water

Vapor pressure, PB^o, of pure butane is 2.3966 atm at 25 degrees C and that of n-pentane, Pp^o, is
0.6999 atm at 25 degrees C. Using Raoult's Law, calculate partial vapor pressure of n-butane (MW 58.12)
and n-pentane (MW 72.15) in mixture of 50 g of each of 2 vapors at 25 degrees C in atom and
pounds/in^2 (psi)

p1 = p1^o x X1
p2 = p2^o x X2
p = p1 + p2
mole fraction = n1/(n1 + n2)
1 atm = 14.7 psi

50 g butane x 1 mole butane/58.12 g butane = 0.8603 mole butane

50 g n-pentane x 1 mole n-pentane/72.15 g pentane = 0.693 mole n-pentane
mole fraction butane = 0.8603 mole butane/(0.8603 mole butane + 0.693 mole pentane) = 0.5539 mole
fraction butane
mole fraction n-pentane = 0.693 mole n-pentane/(0.8603 mole butane + 0.693 mole n-pentane) =
0.4461 mole fraction n-pentane
butane = p1 = 2.3966 atm x 0.5539 mole fraction butane = 1.3274 atm
1.3274 atm x 14.7 psi/1 atm = 19.514 psi = partial pressure of butane at 25 degree C
n-pentane = p2 = 0.6999 atm x 0.4461 mole fraction n-pentane = 0.31226 atm
0.31226 atm x 14.7 psi/atm = 4.59 psi = partial pressure of n-pentane at 25 degree C

a) Compute freezing point depression of 1 g methylcellulose (MW = 26,000 g/mole) dissolved in 100 g
water
b) Using van't Hoff equation, compute osmotic pressure of this solution at 20 degrees C. Express results
in cm of solution. Convert mmHg to mm of solution by mm solution = mmHg x density of Hg/density of
solution. Density of mercury at 20 degrees C is 13.5462 g/mL. Density of solution is 1 g/mL
c) Assume you have a thermometer which is able to accurately read 0.05 degrees C & estimate value to
0.005 degrees C. Can you use freezing point depression of methylcellulose solution to determine MW of
polymer? Can you use osmotic pressure to obtain molecular weight?

a) deltaTf = kfm2
m = moles/kg solvent
1 g methylcellulose x 1 mole methylcellullose/26,000g methylcellulose = 3.846 x 10^-5 mole
methylcellulose
100 g water x 1 kg/100g = 0.1 kg water
3.846 x 10^-5 mole methylcellulose/0.1 kg water = 3.846 x 10^-4 m
deltaTf = 1.86 Kg x K/mol x 3.846 x 10^-4 moles/kg methylcellulose = 7.15 x 10^-4 degrees C

b) 20 degrees C + 273 = 293 K

Osmotic pressure = II = [Csolutes]RT
II = 3.846 x 10^-5 mole methylcellulose/(100 mL x 1 L/1000mL) x 62.36367((L x mmHg)/(K x mol)) x 293 K
= 7.0276 mmHg
7.0276 mmHg x ((13.5462 g/mL mmHg)/(1 g solution/mL)) = 95.1976 mm of solution x 1 cm/10 mm =
9.51976 cm of solution

c) Freezing point depression is too small to read on most thermometers. Should use osmotic pressure to
determine molecular weight of methylcellulose
Osmotic pressure of solution of urea (MW 60) with 0.3 g of drug in 50 mL of water at 20 degrees C.?
(Use Van't Hoff eq)

II = [Csolutes]RT

0.3 g urea x 1 mole urea/60 g urea = 0.005 mole urea/0.05 L water = 0.1 mole/L urea
50 mL water x 1 L/1000 mL = 0.05 L water

20 degrees C + 273 = 293 K

II = 0.1 mole urea/L urea x 0.08205746 (L x atm)/(mol x K) x 293 K = 2.4 atm

1 fluid ounce (29.573 mL) solution contains 4.5 grains (291.6 mg) of silver nitrate (E = 0.33). How much
sodium nitrate (E = 0.68) must be added to this solution to make isotonic nasal fluid (0.9% NaCl)?

0.9g NaCl/100 mL solution x 29.573 mL solution = 0.266157 g NaCl total needed

0.33 g NaCl/1 g silver nitrate x 0.2916 g silver nitrate = 0.096228 g NaCl equivalents
0.266157 g total NaCl - 0.096228 g NaCl equivalents = 0.169929 g NaCl needed
0.68 g NaCl/1 g sodium nitrate x Y = 0.169929 g NaCl equivalents needed
Y = 0.2499 g sodium nitrate x 1000 mg/g = 250 mg sodium nitrate

Using sodium chloride equivalent method, make following solutions isotonic with respect to the mucous
lining of eye
a) Tetracaine HCl (E = 0.18): 10 g, NaCl qs, sterile water qs ad 1000 mL
b) Tetracaine HCl: 0.1g, boric acid (E = 0.5) qs, sterile water qs ad 10 mL

a) 0.9 g NaCl/100 mL solution x 1000 mL solution = 9 g NaCl needed total

0.18 g NaCl/1 g tetracaine HCl x 10 g tetracaine HCl = 1.8 g NaCl equivalents
9 g NaCl total -1.8 g NaCl from tetracaine HCl = 7.2 g NaCl needed

b) 0.9 g NaCl/100 mL solution x 10 mL solution = 0.09 g NaCl needed total

0.18 g NaCl/1 g tetracaine HCl x 0.1 g tetracaine HCl = 0.018 g NaCl equivalents
0.5 g NaCl/1 g boric acid x Y = 0.072 g NaCl = 0.144 g boric acid needed

Osmotic pressure includes

A semi-permeable membrane allows small solvent molecules to diffuse across, but NOT large solute
molecules

Osmosis

Process where small solvent molecules diffuse through a semi-permeable membrane from a more
concentrated solution into less concentrated solution

Osmotic pressure is

the pressure that must be applied to the side of the concentrated solution to prevent the flow of the
pure solvent into the solution

Osmotic pressure (II) is given by:

Van't Hoff equation:
II = RTc
c = concentration in mol/L (molarity)
1) II depends on concentration, but not solute type
2) Valid for dilute solutions (or ideal solutions)

Morse equation:
II = RTm
m = concentration in mol/1 kg of water (molality)

Osmotic drug delivery systems

See slide 36 Colligative Properties Solutions

Has an impermeable, but flexible inner membrane

Semipermeable outer membrane

Water flows in, causing drug to release, by making inner layer collapse and pushes drug out

Hypertonic

solution has greater concentration than inside red blood cells

Isotonic

solution has equal concentration to inside red blood cells

Hypotonic

solution has less concentration than inside red blood cells

Solution with osmotic pressure the same as that of body fluid is called

isotonic

Solutions with ___________ are isotonic with bodily fluids

0.9% NaCl (or 5% dextrose)

Tonicity

The osmotic pressure of solution (can be adjusted by controlling concentration of solutes)

Isotonicity

state where osmotic pressure of pharmaceutical solution is equal to that of physiological fluids

Minimizes discomfort/irritation during drug administration via sensitive membranes of organs (ex:
ophthalmic and nasal)

1.9% w/w solution of boric acid is ______ but not ________

isosmotic with blood, isotonic to blood

Boric acid and some other agents (ex: urea, ammonium chloride, alcohol, glycerin) will

penetrate RBC's plasma membrane

As a result, these compounds cannot be used for tonicity adjustment for IV injections

Can still be used for preparing pharm solutions for nose and eye treatments (difficult membranes)

Preparations of Isotonic Solutions: Methods

0.9% NaCl is isotonic (deltaTf = 0.52 degrees C)

Methods:
1) NaCl equivalent method (E-value)
2) Freezing Point depression method (D-value)
3) Isotonic Solution method (V-values)

All methods depend on osmotic pressure being colligative property (change in osmotic pressure is
additive)
All methods require use of tables, because most pharmaceutical solutions are NOT ideal (II = cRT does
not work)

NaCl Equivalent Method (E-value)

E-value of a drug: the weight of NaCl that produces the same osmotic pressure as 1 g of drug

E value of dexamethasone sodium phosphate is 0.17 (at 1%)

The osmotic pressure of 1 g of dexNaPhos is equivalent to 0.17 g NaCl

Because 0.9 g/100 mL of NaCl is isotonic with blood, then a 1% (1 g/100 mL) solution of DexNaPhos is
hypotonic (it is "short" by 0.9 - 0.17 = 0.73 g of NaCl)

How much NaCl should we add to 1% DexNaPhos to make it isotonic?

0.73 g

Calculate amount (in grams) of NaCl (MW 58.5) required to make 250 mL of 0.5% w/v solution of
Lidocaine HCl (MW 270.8) that is isotonic with blood. The E-value of Lidocaine HCl is 0.22

0.5% w/v = 0.5g/100 mL

Osmotic equivalent of 0.5 g Lidocaine HCl in 100 mL solution = 0.5 x 22 = 0.11 g of NaCl

Isotonic saline solution (0.9% NaCl) contains 0.9 g of NaCl in each 100 mL of solution

Amount of NaCl needed to make 100 mL of Lidocaine HCl isotonic is: 0.9 - 0.11 = 0.79 g NaCl

For 250 mL isotonic solution = 0.79 x 250/100 = 1.975 g of NaCl

How much dextrose monohydrate (E value 0.16) will be needed to create 250 mL of isotonic Lidocaine
HCl

For 250 mL of isotonic Lidocaine HCl solution using NaCl = 1.975 g NaCl will be needed

For 250 mL of isotonic Lidocaine HCl solution using dextrose monohydrate (E value 0.16)

1.975 g/0.16 = 12.3 g of dextrose needed

Freezing point depression method

0.9% NaCl is isotonic (deltaTf = 0.52 degrees C)

D value is freezing point depression (degrees C) for given drug concentration

Ex: DexNaPhos has D value of 0.05 degree C/0.5% concentration

Isotonic Solution Method (V-Values)

V value: volume of water needed to make 0.3 g of drug isotonic
Some tables are for 1 g of drug
For DexNaPhos, the V value is 18.9 mL
To make 100 mL of 1% DexNaPhos solution, add 18.9 mL of water to 1 g drug and qs with an isotonic
solution (ex: 0.9% NaCl)

Steps for calculating tonicity adjusting agents

1) Calculate the total amount of NaCl required to make an isotonic solution

2) Calculate NaCl equivalent of existing components in the prescription
3) Calculate the amount of NaCl equivalent required to reach the total amount
4) Calculate the amount of adjusting agent that provides the missing amount of NaCl equivalent

One gram of sucrose is dissolved in 100 mL of solution at 25 degrees C. What is the osmotic pressure of
the solution? Would this solution be hypotonic, isotonic or hypertonic with respect to red blood cells?

1 g/0.1 L x mol/342.3 g = 0.0292 mol/L = 0.0292 M

II - RTc = (0.0821 L x atm/K x mol) x (298K) x (0.0292 mol/L) = 0.71 atm

A solution of "normal" saline is considered isotonic with red blood cells

0.9% = 0.9g/100 mL = 0.9 g/0.1 L x mol/58.44 g = 0.154 mol/L

IIRTc = (0.0821 L x atm/K x mol) x (298K) x (0.308 mol/L) = 7.53 atm

(since NaCl is almost completely dissociated into two ions, for the purposes of colligative properties, one
needs to take account the 0.154 mol/L actually represents 0.308 mol/L (2 x 0.154))

The sucrose is hypotonic with respect to RBCs.

How many mg of boric acid (E value = 0.5) should be used in compounding this prescription?
Zinc Sulfate 0.06 g (E value 0.15), Boric acid qs, purified water ad 30 mL, make isotonic solution)

0.9 g NaCl/100 mL x 30 mL = 0.27 g NaCl needed

0.15 g NaCl/1 g zinc sulfate x 0.06 g zinc sulfate = 0.009 g NaCl equivalents

0.27 g NaCl needed - 0.009 g NaCl equivalents = 0.261 g NaCl to make isotonic

0.5 g NaCl/1 g boric acid x Y = 0.261 g

Y = 0.522 g boric acid

How many grams of sodium chloride should be used in preparing the solution?
Dextrose, anhydrous 2.5% (E value 0.18), NaCl qs, sterile water for injection ad 1000 mL

0.9 g NaCl/100 mL x 1000 mL = 9 g sodium chloride needed

2.5 g dextrose/100 ml x 1000 mL = 25 g dextrose
0.18 g NaCl/1 g dextrose x 25 g dextrose = 4.5 g NaCl equivalents by dextrose

9 g - 4.5 g = 4.5 g of additional NaCl needed to make solution isotonic

How many grams of boric acid should be used in compounding this prescription?
Tetracaine HCl 0.1 g (E value 0.18), Zinc sulfate 0.05 g (E value 0.15), boric acid qs (E value 0.5), purified
water 30 mL, make isotonic

0.9 g NaCl/100 mL x 30 mL = 0.27 g NaCl

0.18 g NaCl/1 g tetracaine HCl x 0.1 gtetracaine HCl = 0.018 g NaCl equivalents

0.15 g NaCl/1 g zinc sulfate x 0.05 g zinc sulfate = 0.0075 g NaCl equivalents

Need 0.27 g - 0.018 g - 0.0075 g = 0.2445 g NaCl

0.5 g NaCl/1 g boric acid x Y = 0.2445 g NaCl

Y = 0.489 g boric acid

hermodynamics

the study of the energy and its transformations

Thermochemistry

the study between the relationship between chemical energy and energy changes

Energy

the ability to do work or transfer heat

Work

energy used to cause an object that has mass to move

Heat

energy used to cause the temperature of an object to rise

Kinetic Energy

is energy an object possesses by virtue of its motion

Potential Energy
is energy an object possesses by virtue of its position or chemical composition

Electrostatic Potential Energy

the most important form of potential energy in molecules is electrostatic potential energy
(d = distance between particles, Q = charges of particles)

Joule (J)

SI unit of energy

cal --> Joules

1 cal = 4.184 J
1 Cal (food) = 1000 cal (chemistry)

System

includes the molecules we want to study (what is doing the reaction)

Surroundings

everything else besides the system (environment)

Work equation

w = F x d (w = work, F = force, d = distance over which the force is exerted)

What does temperature measure?

kinetic energy

How does heat flow?

from warmer objects to cooler objects

(however, cold does not transfer to hot objects)

Conversion of Energy

energy can be converted from one type to another

First Law of Thermodynamics

-energy is neither created nor destroyed

-the total energy of the universe is constant; if the system loses energy, it must be gained by the
surroundings, and vice versa

Internal Energy

the sum of all kinetic and potential energies of all components of the system; we call it E
(final energy minus the initial energy of the system)

Exothermic

losing energy (-Q)

Endothermic

gaining energy (Q)

Changes in Externam Energy

change in energy = q + w

delta e, q, w and their signs

+q = system gains heat

-q = system loses heat
+w = work done on the system
-w = work done by the system
+delta e = net gain of energy by system
-delta e = net loss of energy by system

When heat is absorbed by the system from the surroundings, the process is

endothermic (absorbing of heat)

When heat is released by the system into the surroundings, the process is

exothermic (releasing of heat)

Force

is a push or pull on an object

Work equation

is the product of force applied to an object over a distance

The internal energy of a system is __________ of the path by which the system achieved that state

independent

State Function

depends only on the present state of the system, not on the path by which the system arrived at that
state
-change of energy depends only on the initial energy and the final energy (ex. internal energy)

What are not state functions?

q and w

Equation to measure the work done by the gas if the reaction is done in a vessel that has been fitted
with a piston

w = -P(change V)

(work = negative pressure(change volume))

Enthalpy

heat produced or released in a chemical reaction

extensive
Q

What is the equation of entalpy (delta H) if it is done at a constant temperature?

delta H = Hproducts - Hreactants

Calorimeter

instrument used to measure heat flow

Heat Capacity

the amount of energy required to raise the temperature of a substance by 1 K (1 degree C) (usually given
for one mole of the substance)
Specific Heat

the amount of energy required to raise the temperature of 1 g of a substance by 1 K (1 degree C)

Constant Pressure Calorimetry

we can calculate delta H for the reaction with this equaltion (Q = mc(delta t)

molar heat capactiy

how much heat does it take for a mol of a substance to heat up

Bomb Calorimetry

-normally a combustion reation

-volume is constant
-measure the change of internal energy
-most of the times the difference is very small

Enthalpy/Entropy

-enthalpy is the heat absorbed by a system during a constant-pressure process

-entropy is a measure of the randomness in a system
-both play a role in determining whether a process is spontaneous

Spontaneous Processes

-proceed without any outside assistance

-processes that are spontaneous in one direction are nonspontaneous in the reverse direction

Experimental Factors Affect Spontaneous Processes

-temperature and pressure can affect spontaneity
-an example of how temperature affects spontaneity is ice melting or freezing

Reversible Processes

-the system changes so that the system and surroundings can be returned to the original state by exactly
reversing the process
-this maximizes work done by a system on the surroundings
-delta S(universe) = delta S(system) + delta S(surroundings) = 0

Irreversible Processes

-cannot be undone by exactly reversing the change to the system or cannot have the process exactly
followed in reverse
-also, any spontaneous process is irreversible
-delta S(universe) = delta S(system) + delta S(surroundings) > 0

Entropy (S)

-can be thought of as a measure of the randomness of a system

-is a state function (delta S = Sfinal - Sinitial)
-it can be found by heat transfer from surroundings at a given temperature ((delta S =
q(environment))/temperature
(must be constant T)

Second Law of Thermodynamics

-the entropy of the universe increases in any spontaneous processes

Entropy Change

since entropy is a state function, the final value minus the initial value will give the overall change

Molecular Motions

-molecules exhibit several types of motion (translational, vibrational, rotational)

Translational Motion

movement of the entire molecule from one place to another

Vibrational Motion

periodic motion of atoms within a molecule

Rotational Motion

rotation of the molecule about an axis

Entropy and Physical States

-entropy increases with the freedom of motion of molecules
-entropy of a system increases for processes where gases form from either solids or liquids, liquids or
solutions form from solids, or the number of gas molecules increases during a chemical reaction

Third Law of Thermodynamics

-the entropy of a pure crystalline substance at absolute zero is 0

-consider all atoms or molecules in the perfect lattice at 0 K

Standard Entropies

-the reference for entropy is 0 K, so the values for elements are not 0 J/mol(K) at 298 K
-standard molar entalpy for gases are generally greater than liquids and solids (be careful of size)
-standard entorpies increase with molar mass
-standard entropies increase with number of atoms in a formula

Entropy Changes

-entropy changes for a reaction can be calculated in a manner analogous to that by which delta H is
calculated
-where n and m are the coefficients in the balanced chemical equation

Entropy Changes in Surroundings

-heat flows into or out of the system changes the entropy of the surroundings

Isothermal Process (entropy)

Subscript

A number in a chemical formula that tells the number of atoms in a molecule or the ratio of elements in
a compound
TERM

Coefficient

DEFINITION

A number in front of a chemical formula in an equation that indicates the relative number of moles of
reactants and products involved in a reaction.

+ 1 more side

Percent composition

the percent by mass of each element in a compound

Law of conservation of mass

Lavoisier
Matter is neither created nor destroyed

Mole ratio

fraction formed from the coefficients in a balanced chemical equation.

Avogadro's Number
number of representative particles in a mole, 6.02 X 10^23

Synthesis

A+B=AB

Decomposition

A chemical reaction that breaks down compounds into simpler products.

AB = A + B

Single Replacement

A + BC --> B + AC

Double Replacement

a chemical reaction where two elements in different compounds trade places

Combustion

Burning. Oxygen gas is one of the reactants and water is one of the products.

Activity Series

A list of elements organized according to the ease with which the elements undergo certain chemical
reactions.

Products

The elements or compounds produced by a chemical reaction. On the right side of a chemical equation.

Reactants

A starting material in a chemical reaction. On the left side of a chemical equation.

TERM

Stoichiometry

DEFINITION

(chemistry) expresses the quantitative relationship between reactants and products.

+ 1 more side
Percent yield

the ratio of the actual yield to the theoretical yield, multiplied by 100

Theoretical yield

the maximum amount of product that can be produced from a given amount of reactant ... the
calculated amount of product in a stoichiomety problem.

Limiting reactant

the substance that is consumed completely - controls the quantity of product that can form in a
chemical reaction. Can be determined by calculating the mass of a single product formed from each
reactant.

Excess reactant

The substance that is not used up completely in a reaction

Actual yield

The measured amount of a product obtained from a reaction. Must be determined experimentally in the
lab.
Molar Mass

The mass of 1 mole of any substance. Must use the periodic chart to obtain this value.
units: g/mol

Balanced Chemical Equation

Allows one to determine the mole ratio of any two substances in the reaction

Generally less than theoretical yield

Most of the time, actual yield of a chemical reaction is . . .

1st step in a stoichiometry problem

write a balanced chemical equation

mass of one mole of a diatomic element (hydrogen, nitrogen, oxygen, fluorine, chlorine, bromine,
iodine)

twice the mass listed for that element on the periodic chart

mass of one mole of a compound

the sum of the masses listed on the periodic chart of the atoms contained in it

Conversion Factor

a ratio of equivalent measurements used to convert a quantity from one unit to another
Empirical formula

Simplest positive integer ratio of atoms present in a compound

Molecular Formula

A formula that gives the number of each atom that is present in any given compound.

Law of definite proportions

a compound is always composed of the same elements in the same proportion by mass, no matter how
large or small the sample.

How many moles of O2 are needed for 0.1 moles of C4H10 to react completely?

2C4H10 + 13O2* 8CO2 + 10H2O

How many moles of Fe2O3 could be produced if 28 grams of Fe is reacted to completion with excess
O2?

4Fe + 3O2* 2Fe2O3

If 138g NO2 and 48g O2 are reacted, what mass (in grams) of N2O5 is produced if there is a 90% yield?

4NO2 + O2 2N2O5

Answer: 146
How many oxygen atoms are there in 2.2 moles of Al(NO3)3?

If 51g PH3 is produced when 62g P and 10g H2 are mixed, what is the percent yield?

2P + 3H2* 2PH3

Dividing the number of moles of each reactant by its coefficient in the balanced reaction
reveals that P is the limiting reagent.

How many moles of oxygen atoms are there in 350g CaCO3?

What is the maximum number of moles of water that could be produced when 4 moles of C5H12 are
reacted with excess O2?

C5H12 + 8O2* 5CO2 + 6H2O

How many grams of Fe2O3 could be produced if 3 moles of Fe is reacted to completion with excess O2?

4Fe + 3O2* 2Fe2O3

If 9 moles Ba(OH)2 and 7 moles H3PO4 react completely, what is the maximum number of moles of
Ba3(PO4)2 that could be produced?

3Ba(OH)2 + 2H3PO4* Ba3(PO4)2 + 6H2O

9 moles Ba(OH)2 and 7 moles H3PO4 react completely, what is the limiting reagent?
3Ba(OH)2 + 2H3PO4* Ba3(PO4)2 + 6H2O

Ba(OH)2

What mass (in grams) of PCl3 could be produced if 142g Cl2 is reacted completely with excess P?

2P + 3Cl2* 2PCl3

How many hydrogen atoms are there in 24 grams of (NH4)2CO3?

What is the maximum number of moles of CO2 that could be produced when 28 moles of O2 are
reacted with excess C5H12?

C5H12 + 8O2 5CO2 + 6H2O

How many grams of sulfur are there in 15.9 grams of Cu2S?

Thermochemistry

The study of the relationships between chemistry and energy

Heat

The flow of energy caused by a temperature difference

Kinetic energy

Energy of motion

Thermal energy

Energy associated with the temperature of an object

Potential energy

Energy associated with the position or composition of an object

Chemical energy

Energy associated with the relative positions of electrons and nuclei in atoms and molecules

Law of conservation of energy

Energy cannot be created nor destroyed

System

The portion of the universe that is singled out for investigation

Surroundings

Everything with which the system can exchange energy

Joule

SI unit of energy

calorie

Amount of energy required to raise the temperature of 1 g of water by 1 C

Calorie

Same as a kilocalorie

Kilowatt-hour

Energy unit used to express large amounts of energy

First law of thermodynamics

The total energy of the universe is constant

Internal energy

Sum of the kinetic and potential energies of all the particles that compose the system

Thermal equilibrium

Point at which there is no additional transfer of heat

Thermal Changes and Heat Capacity

When a system absorbs heat, its temperature changes by T

Heat capacity

Quantity of heat required to change its temperature by 1 C

Specific heat capacity

The amount of heat required to raise the temperature of 1 mole of a substance by 1 C

Pressure- volume work

Occurs when the force is caused by a volume change against external pressure

Calorimetry

Measures the thermal energy exchanged between the reaction and the surroundings by observing the
change in temperature of the surroundings
Bomb calorimeter

A piece of equipment designed to measure energy for combustion reactions

Enthalpy

The sum of its internal energy and the product of its pressure and volume

Endothermic reaction

Absorbs heat from its surroundings

Exothermic reaction

Gives off heat to its surroundings

Enthalpy of reaction (heat of reaction)

The enthalpy change for a chemical reaction

Coffee-cup calorimeter

A piece of equipment designed to measure the change in enthalpy for reactions at constant pressure

Hess's Law

A chemical equation can be expressed as the sum of a series of steps, then Hrxn for the overall equation
is the sum of the heats of reactions for each step

Standard state

Gas: pure gas at 1 atm

Liquid or solid: pure substance at 1 atm and the temperature of interest (usually 25 C)
Substance in solution: 1 M

Standard enthalpy change

The change in enthalpy for a process when all reactants and products are in their standard states

Standard enthalpy (heat) of formation

The change in enthalpy when 1 mol of a compound forms from its constituent elements in their
standard states

Thermochemistry

The study of the relationships between chemistry and energy

Heat

The flow of energy caused by a temperature difference

Kinetic energy

Energy of motion
Thermal energy

Energy associated with the temperature of an object

Potential energy

Energy associated with the position or composition of an object

Chemical energy

Energy associated with the relative positions of electrons and nuclei in atoms and molecules

Law of conservation of energy

Energy cannot be created nor destroyed

System

The portion of the universe that is singled out for investigation

Surroundings

Everything with which the system can exchange energy

Joule

SI unit of energy

calorie

Amount of energy required to raise the temperature of 1 g of water by 1 C

Calorie

Same as a kilocalorie

Kilowatt-hour

Energy unit used to express large amounts of energy

First law of thermodynamics

The total energy of the universe is constant

Internal energy

Sum of the kinetic and potential energies of all the particles that compose the system

Thermal equilibrium

Point at which there is no additional transfer of heat

Thermal Changes and Heat Capacity

When a system absorbs heat, its temperature changes by T

Heat capacity
Quantity of heat required to change its temperature by 1 C

Specific heat capacity

The amount of heat required to raise the temperature of 1 mole of a substance by 1 C

Pressure- volume work

Occurs when the force is caused by a volume change against external pressure

Calorimetry

Measures the thermal energy exchanged between the reaction and the surroundings by observing the
change in temperature of the surroundings

Bomb calorimeter

A piece of equipment designed to measure energy for combustion reactions

Enthalpy

The sum of its internal energy and the product of its pressure and volume

Endothermic reaction

Absorbs heat from its surroundings

Exothermic reaction

Gives off heat to its surroundings

Enthalpy of reaction (heat of reaction)

The enthalpy change for a chemical reaction

Coffee-cup calorimeter

A piece of equipment designed to measure the change in enthalpy for reactions at constant pressure

Hess's Law

A chemical equation can be expressed as the sum of a series of steps, then Hrxn for the overall equation
is the sum of the heats of reactions for each step

Standard state

Gas: pure gas at 1 atm

Liquid or solid: pure substance at 1 atm and the temperature of interest (usually 25 C)
Substance in solution: 1 M

Standard enthalpy change

The change in enthalpy for a process when all reactants and products are in their standard states

Standard enthalpy (heat) of formation

The change in enthalpy when 1 mol of a compound forms from its constituent elements in their
standard states

What happens when a compound that is made of ions dissolves in water?

The ions separate from one another (dissociation)

Write the equation for the dissolution of aluminum sulfate, Al2(SO4)3 , in water. How many moles of
aluminum ions and sulfate ions are produced by dissolving 1 mol of aluminum sulfate? What is the total
number of moles of ions produced by dissolving 1 mol of aluminum sulfate?

a. 1 mol Al2(SO4)3 → 2 mol Al^3+ + 3 mol SO4^2−

b. 2 mol Al^3+ + 3 mol SO4^2− = 5 mol of solute ions

Write the equation for the dissolution of each of the following in water, and then determine the number
of moles of each ion produced as well as the total number of moles of ions produced.
a. 1 mol ammonium chloride
b. 1 mol sodium sulfide
c. 0.5 mol barium nitrate

a. NH4Cl(s) ------> NH4^+(aq) + Cl^−(aq); 1 mol NH4^+, 1 mol Cl^−, 2 mol ions
b. Na2S(s) ------> 2Na^+(aq) + S^2−(aq); 2 mol Na^+, 1 mol S^2−, 3 mol ions
c. Ba(NO3)2(s) ------> Ba^2+(aq) + 2NO3^− (aq); 0.5 mol Ba^2+, 1 mol NO3^−, 1.5 mol ions

Most phosphates are __________

a. soluble
b. insoluble

b. insoluble

Will a precipitate form when solutions of ammonium sulfide and cadmium nitrate are combined?

Yes. Ammonium nitrate remains in solution and

cadmium sulfide precipitates.

Find the complete and net ionic equations of

(NH4)2S (aq) + AlPO4 (aq).

Complete: 6NH4^+(aq) + 2S^2- (aq) +2Al^3+ (aq) + 2PO4^3-(aq) ------> Al2S3 (s) + 6NH4^+ (aq) +
2PO4^3- (aq)
Net: 2S^2- (aq) +2Al^3+ (aq) ------> Al2S3 (s)

Will a precipitate form if solutions of potassium nitrate and magnesium sulfate are combined? If so,
write the net ionic equation for the reaction.

No.
How and why does adding a nonvolatile, electrolyte substance affect the vapor pressure?

It decreases because there is less water molecules on the surface. This means that less water molecules
can leave the liquid and become a gas

How and why does adding a nonvolatile, electrolyte substance affect the freezing point?

It decreases because the solute particles interfere with the attraction between solvent particles

How and why does adding a nonvolatile, electrolyte substance affect the boiling point?

It increases because more heat will be required to raise the vapor pressure of the solution to equal the
atmospheric pressure

How and why does adding a nonvolatile, electrolyte substance affect the osmotic pressure?

The solute molecules on the solution side allow fewer water molecules to strike the membrane so the
rate at which water molecules leave the pure water side is greater than the rate at which they leave the
solution. This causes the level of the solution to rise

t takes 55.0J to raise the temperature of an 9.90 g piece of unknown metal from 13.0
C to 24.1C. What is the specific heat for the metal?

.501j/gC

The molar heat capacity of silver is 25.35 J/molC . How much energy would it take to
raise the temperature of 9.90g of silver by 16.8C?

39J

what is the specific heat of silver?

M Ag=107.87g/mol
.235 J/gC

A calorimeter contains 25.0 mL of water at 11.5 C. When 1.30 g of X (a substance with

a molar mass of 64.0 ) is added, it dissolves via the reaction
X (s) + H₂0 →X (aq)
and the temperature of the solution increases to 28.5 C. Calculate the enthalpy
change, , for this reaction per mole of X.
Assume that the specific heat and density of the resulting solution are equal to those
of water [4.18 J/gC and 1.00 g/mL] and that no heat is lost to the calorimeter itself,
nor to the surroundings.

-92 kJ/mol

C₁₂H₂₂O₁₁ + 12O₂ → 12CO₂ + 11H₂O

10.0 of sucrose, , was burned in a bomb calorimeter with a heat capacity of 7.50 . The
temperature increase inside the calorimeter was found to be 22.0 . Calculate the
change in internal energy, , for this reaction per mole of sucrose

-5650 kJ/mol

A total of 2.00mol of a compound is allowed to react with water in a foam coffee cup
and the reaction produces 101 g of solution. The reaction caused the temperature of
the solution to rise from 21.0 to 24.7 C. What is the enthalpy of this reaction? Assume
that no heat is lost to the surroundings or to the coffee cup itself and that the specific
heat of the solution is the same as that of pure water.

-.782kJ/mol

In the following experiment, a coffee-cup calorimeter containing 100 mL of water is

used. The initial temperature of the calorimeter is 23.0 C. If 3.50 g of CaCl₂ is added to
the calorimeter, what will be the final temperature of the solution in the calorimeter?
The heat of solution of is Cacl₂ is -82.8 kJ/mol.

29degrees

A piston has an external pressure of 9.00 atm. How much work has been done if the
cylinder goes from a volume of 0.180 liters to 0.650 liter

-428J

The combustion of hydrogen-oxygen mixtures is used to produce very high

temperatures (approximately 2500 °C) needed for certain types of welding operations.
Consider the reaction to be
H₂ + 1/2O₂ → H₂O
standard enthalpy change = -241.8kJ
What is the quantity of heat evolved, in kilojoules, when a 210g mixture containing
equal parts of H₂ and O₂ by mass is burned
1590 kJ

given grams of X and grams of H20 mixed in a styrofoam cup; given temperature
change, what is the heat of solution in kJ/mol X; heat of solution = enthalpy change =
q

#39 and mastering chem #3