CHEM 16.

1 REVIEWER
A. Experiment #6: Calorimetry
B. Experiment #7: Paper Chromatography
C. Experiment #8: Dynamic Equilibrium and Heats of Solution
D. Experiment #9: Distillation of Rubbing Alcohol
E. Experiment #10: Gases
F. Experiment #11: Colligative Properties
G. Experiment #12: pH, Conductivity, and Relative Strengths of Acids and Bases

Calorimetry
• process of measuring the amount of heat released or absorbed during a chemical reaction
• 1st law of thermodynamics: the total internal energy of the universe is constant = energy can
neither be created nor destroyed, it can only be converted from one form to another
o Law of Conservation of Energy = universe is an isolated system
Types of Calorimetry
• Constant Pressure Calorimetry = Coffee Cup Calorimeter or Styroball Calorimeter
• Constant Volume Calorimetry = Bomb Calorimeter
Calorimetry set-up

HCl + NaOH ® NaCl + H2O

Adiabatic system: no transfer of heat from the system to the surroundings

• Placed an insulator = Styrofoam ball
o No easy absorbance/release of heat from the system
o Very low heat capacity
§ Heat capacity = tendency to absorb/release heat

qisolated system = qrxn + qcal qrxn = (∆Hrxn)(nLR)

qrxn + qcal = 0 qcal = C∆T ; where C = mc or nCm
Thus, qrxn = -qcal Thus, (∆Hrxn)(nLR) = -Ccal∆T

If (+) ∆H à absorbed heat à Endothermic; temperature decreases

If (-) ∆H à gives off heat à Exothermic; temperature increases
Procedure
Calibration (Determining heat capacity of calorimeter)
• Ccal is highly dependent on the amount of matter
• Need to calibrate because Ccal is not constant in all styrofoams; and in test tubes
• ∆Hrxn of HCl + NaOH ® NaCl + H2O = -55.85 kJ/mol
"∆#$%& ∙()*
o Ccal =
∆+
Determination of ∆Hrxn
"/012⋅∆+
• ∆𝐻-.( = (
)*
• HCl + NaOH ® NaCl + H2O and HNO3 + NaOH ® NaNO3 + H2O should have the same ∆Hrxn
given that they both have the same NIE (H+ + OH- ® H2O)
Troubleshooting
• There should be no space in between the test tube and the Styrofoam so the heat will not escape
• Don’t change test tubes/styrofoams in the course of the experiment because the amount of matter
calibration will change as well

Paper Chromatography
Chromatography
• “chroma” + “graphein” = to illustrate/write color
• A technique for separation of mixture
• Developed by Mikhail Tsvet
o In his experiment, he added plant extracts (with color) on top of calcium carbonate
powder. Then he added water to it and after all water has passed on the packed
powder, separation of color is formed
o Each color corresponds to a certain compound
• Types of Chromatography
o Column Chromatography and Planar Chromatography

Chromatographic Set-up
• Mobile Phase
o Moving part (H2O)
• Stationary phase
o Staying part (paper)
• Sample mixture
o To be separated
How does separation occur?
• Two competing factors: There is a competition between the attraction of the sample to the
solvent and to the paper.
o Solubility to solvent (mobile phase)
o Adsorption to paper (stationary phase)
• For paper chromatography
o Higher solubility to solvent: moving faster
o Higher adsorption to stationary phase: moving slowly
• Primary reason of solubility and adsorption: intermolecular forces of attraction (IMFA)
 • Separation is based on polarity
o Molecular polarity
§ Due to tendencies of some element to attract more electron (electronegativity),
they tend to disrupt electron cloud molecule, which leads to partial charge
formation
o Polarity is dependent on:
§ Electronegativity of atoms
§ Geometry
o General rule of polarity: Like dissolves like
o Derivatives of Polarity: IMFA (arranged according to decreasing strength)
§ Ion-ion
§ Ion-dipole
§ H-bonding
§ Dipole-dipole
§ Ion-induced dipole
§ Dipole-induced dipole
§ London dispersion forces
Intermolecular Forces of Attraction
• London Dispersion Force
o For all types of molecules

• Dipole-induced dipole and Ion-induced dipole

• Dipole-dipole
o Polar + polar

• Hydrogen bonding
o Special type of dipole-dipole (H-O, H-N, H-F)
 • Ion-dipole
o Ion + polar molecules

• Ion-ion
o Ion + ion (ionic)

Types of Chromatography based on polarity of stationary phase

• Normal phase chromatography
o Stationary phase is polar
• Reverse phase chromatography
o Stationary phase is nonpolar
• Experiment made use of a Planar Normal Phase Chromatography (paper chromatography)
o Stationary phase: water adsorbed in cellulose (cellulose is in paper)
o Mobile phase: 1% NaCl solution in water
Paper Chromatography Set-up
 • Chromatographic plate (chromatogram): filter paper with dye spots
o Where the sample mixture to be separated is spotted
o Stationary phase which is the filter paper
• Developing solvent: 1% NaCl solution
o The mobile phase (1% NaCl solution)
o Moves up the stationary phase via capillary actions
• Saturation Filter paper
o Paper added besides the chromatographic plate
o Used to ensure the system inside the chromatogram is saturated (prevent volatilization)
• Chromatographic Chamber: lid + beaker
o Beaker + Lid = Where the chromatographic run is contained
o Must be closed by lid to ensure no solvent would be volatilized

Retention Factor
• Degree of attraction of components to the mobile phase
• If the component is:
o More polar = lower Rf
o More nonpolar = higher Rf

• Rf values are qualitative (used for comparison)

• Based on Rf Values: Allure Red < Sunset Yellow <Tartrazine < Brilliant Blue
• Therefore based on Polarity: Brilliant Blue < Tartrazine< Sunset Yellow< Allure Red

Dynamic Equilibrium and Heats of Solution

Forward vs. Reverse Reaction

When will the forward-reverse reaction stop?

When equilibrium is achieved = stable state.
Dynamic Equilibrium: a state in which the rate of the forward reaction is the same as the rate of the
backward reaction
Chemical equilibrium is achieved when
• Rate of Forward Reaction = Rate of Reverse Reaction
"4[6789:8(:;] "4[>-?4@9:;]
• =
4: 4:
Rate of reactions
• Indicates how fast a reaction occur
• Given by rate of change of concentration over time (derivatives)

Le Chatelier’s Principle
• If a dynamic equilibrium is disturbed, the system would react with the change to attain
equilibrium again (counteract with the change)
• Aims to restore balance
• Proposed by Henry-Louis Le Chatelier
Two types of equilibria
• Acid-base equilibria
o Effect of pH
§ ­pH = ¯H+
§ ¯pH = ­H+
o Color changes are observed
o We collected colored pigments (dyes) which contain anthocyanins that serve as natural
indicators (have similar properties as phenolphthalein)
• Solubility equilibria
o Effect of the nature of solute and solvent (miscible and immiscible)
§ Solubility occurs when the IMFA of the solute-solvent > solute-solute & solvent-
solvent IMFA
§ Ex. Water & oil
• Water-water’s dominant IMFA is H-bonding
• Oil-oil’s dominant IMFA is LDF
• Water-oil’s dominant IMFA is dipole-induced dipole
• H-bonding > Dipole-induced dipole > LDF
• Thus, they would not interact with each other and form an immiscible
liquid
§ Ex. Water & alcohol
• Water-water’s dominant IMFA is H-bonding
• Alcohol-alcohol’s dominant IMFA is H-bonding
• Water-alcohol’s dominant IMFA is H-bonding
• Thus, they would interact with each other and form a miscible liquid
o Change in strength of the IMFA leads to change in the volume of solvent mixture
o System wants to attain highest IMFA possible because it is most stable, and its harder
to break
Acid-base equilibria example
Reaction: H+ + In ßà HIn+
­pH = ¯H+ = reverse reaction
¯pH = ­H+ = forward reaction
𝑝𝐻 = −log [𝐻G ]

When added HCl = forward reaction = ¯pH

H+ + In à HIn+
ln = color A
HIn+ = color B

When added NaOH = reverse reaction = ­pH

H+ + OH- + In à HIn+
H+ + OH- would form water and thus, would lessen H+
HIn+ à H+ + In

Solubility Equilibria
Effect of Nature of Solvent and Solute

Solute and Solvent

Glycerol: (polar; H-bonding)

Naphthalene: (non-polar; LDF)

Sodium Chloride: (ionic; ion-ion)

Water: (polar; H-bonding)

Ethanol: (polar; H-bonding)

Methanol: (polar; H-bonding)

Methanol is more polar than ethanol because the presence of C atoms also affects the polarity of the
molecule. Less C = more polar; More C = more nonpolar

Toluene:
Thus,
• Glycerol + Water = Miscible (both polar)
• Glycerol + Naphthalene = Insoluble (polar and nonpolar)
• Ethanol + Naphthalene = Slightly Soluble (even if ethanol is polar, it still has an ethyl (C2H5)
group that is nonpolar, thus attracting nonpolar solutes)
Effect of Solubility examples
• I2 + H2O will not dissolve completely because I – I interaction is stronger (ion-ion) but will still
dissolve because of I + I Û I2
• I2 + KI in H2O will dissolve because KI + I2 Û I3- (represented by the change in color)
Effect of temperature examples
NH4Cl + water = endothermic (lumamig)
NH4Cl + ∆H Û NH4+ + Cl-
­ temperature = more dissolved = forward reaction

Ca(OH)2 in H2O = exothermic (uminit)

Ca(OH)2 Û Ca2+ + 2OH- + ∆H
¯ temperature = more dissolved = forward reaction
Changes in Volume and Heat
H2O + MeOH (methanol)
∆𝐻;?H@:I?( = J ∆𝐻;?H@:7";?H@:7 + J ∆𝐻;?HL7(:";?H@:7 + J ∆𝐻;?HL7(:";?HL7(:

∆𝐻;?H@:I?( = J[+𝐵𝐵] + J[−𝐵𝐹] + J[+𝐵𝐵]

IMFAsolute-solvent > IMFAsolute-solute + IMFAsolvent-solvent
Thus, it is an exothermic reaction, ­T, ¯V

Acetone + EtOH

Acetone
IMFAsolute-solvent < IMFAsolute-solute + IMFAsolvent-solvent
Thus, it is an endothermic reaction, ¯T, ­V because the substances do not want to interact
Response to IMFA
• ­IMFA = ¯V
• ¯IMFA = ­V
Response to Concentration
• A + B ßà C + D
• More A: forward reaction
o To reduce A, increase C
• More C: reverse reaction
o To reduce C, increase A
Response to Temperature
• Exothermic: A + B à C + heat
o Decrease temperature to form heat
• Endothermic: A + B + heat à C
o Increase temperature to absorb heat, to compensate with high temperature
Response to Pressure
• ¯V, ­P = forward reaction (less gass molecules)
• ­V, ¯P = reverse reaction (more gas molecules)

Distillation of Rubbing Alcohol

Distillation
• Separation of miscible solutions
o Miscible: unsure of the components
• Separation can be done by using the differences in the boiling points of the components
Types of Distillation Set-up
• Simple distillation
o used for separating liquids boiling below 150 °C at 1 atm from either nonvolatile
impurities or another liquid with boiling point that is at least 25 °C from the first
• Vacuum distillation
o used for separating liquids boiling above 150 °C at 1 atm from either non-volatile
impurities or another liquid with boiling point that is at least 25 °C from the first
• Fractional distillation
o used for separating liquids whose boiling points differ by less than 25 °C
• Steam distillation
o used for separating liquids that are insoluble or slightly soluble in water
Simple Distillation set-up
Distilling flask: contains the mixture or solution
How does Distillation occur?
• Due to difference of IMFA of the mixture’s components
o For instance, in Rubbing alcohol, it is composed of H2O and Ethanol/Isopropyl Alcohol
o However, Ethanol/isopropyl alcohol has weaker IMFA compared to water
o Therefore, easier energy is needed to induce evaporation to it
o Thus, it evaporates at lower temp compared to water
Important Notes
• Temperature should not be greater than 100 C because by then, water would also evaporate
• You remove the first mL in the distillate because you assume they’re impurities
• There’s a hole in the condenser for air circulation, to avoid too high pressure that would lead to
the breakage of the glassware
o Because of this, there is an assumed loss of heat (energy is not fully conserved)

Gases
• have weak IMFA, they are loosely connected
• no definite shape/volume; compressible
• have their own
o pressure
o volume
o temperature
o moles
Gas Law Formula Description
Boyle’s Law 𝑃P 𝑉P = 𝑃R 𝑉R At constant T, as ­P, ¯V
Charles’ Law 𝑉P 𝑉R At constant P, as ­V, ­T
=
𝑇P 𝑇R
Gay-Lussac’s Law 𝑃P 𝑃R At constant V, as ­P, ­T
=
𝑇P 𝑇R
Combined Law 𝑃P 𝑉P 𝑃R 𝑉R Obtained by combining Boyle’s,
=
𝑇P 𝑇R Charles’, and Gay-Lussac’s Law
Ideal Gas Law 𝑃𝑉 = 𝑛𝑅𝑇 𝐿𝑎𝑡𝑚
𝑅 = 0.0821
𝑚𝑜𝑙𝐾
Objectives of the experiment
• The presence of gas law: the effect of presence of moles of gas molecules to pressure and
volume and response to temperature
• How to use a eudiometer
o Eudiometer is a classical instrument used to collect gas particles from a reaction to
determine the volume of the gas
Eudiometer
• Same as a barometer
• Solvent: water
• Three cases = three different formulas

ℎ
𝐶𝑎𝑠𝑒 𝐴 = 𝑃:-8ff74 8I- = 𝑃g8- −
13.6
 𝐶𝑎𝑠𝑒 𝐵 = 𝑃:-8ff74 8I- = 𝑃g8-
ℎ
𝐶𝑎𝑠𝑒 𝐶 = 𝑃:-8ff74 8I- = 𝑃g8- +
13.6
* The discrepancy in level of water (represented by h) is due to difference in pressure of the outside
(atmospheric pressure) and inside (pressure of trapped air)
Determining pressure in eudiometer
In the experiment, we were interested in the pressure of captured H2 gas in the reaction of Mg and HCl
Mg + 2HCl à H2 + MgCl2
We are interested in the pressure of H2 only but water has a contribution to pressure due to vapor
pressure
Therefore,
𝑃4-k 8I- = 𝑃:-8ff74 8I- − 𝑃l8:7- L8f?-
Determining Moles (n) of H2 gas
PV = nRT

Colligative Properties
Colligative properties
• Properties of solutions which are dependent on the concentration of solute molecules/ions
• independent from identity of solute
Types of colligative properties
• Boiling Point Elevation (BPE)
• Freezing Point Depression (FPD)
• Vapor Pressure Lowering (VPL)
• Osmotic Pressure (OP)
Relationship of BPE and FPD to Concentration
∆𝑇 = 𝑖𝐾𝑚
∆𝑇g = 𝑖𝐾g 𝑚
∆𝑇n = −𝑖𝐾n 𝑚

Where:
• T = change in temperature compared to original solution
• K = proportionality constant (different for BP and FP)
o Kf of water= 1.86 C/m
o Kb of water = 0.512 C/m
o Dependent to solvent, not solute
o Determined empirically
• m = molality
o?H7; ;?H@:7
o 𝑚 = pq ;?HL7(:
• i = Van’t Hoff factor
o Ratio between the actual concentration of particles produced when the substance is
dissolved and the concentration of a substance as calculated from its mass
o Van’t Hoff Factor is dependent on the type of electrolyte the solute is
§ For Strong Electrolytes, i = total ions it produces upon dissolution
§ For Weak Electrolytes, i = less than the total ions it produces upon dissolution
 § For Non-electrolytes, i = 1
§ Example: (NH4)3PO4, i = 4
• (-) sign for FPD designates its decrease
Thus:
• Boiling Point Elevation
o ∆T is (+) “elevation” à harder to boil
• Freezing Point Depression
o ∆T is (-) “depression” à harder to freeze
Determination of i
∆+
• 𝑖 = ∆+ rstuvws&
&s&xtxyv$stzvx
• 𝑖 = 2 theoretically in the experiment
• 𝑖 > 2, due to instrumental errors
• 𝑖 < 2, due to high molality concentration; oversaturated solutions (this is why we’d rather have
diluted/unsaturated solutions)
Addition of salt to the ice bath
• Salt decreases the freezing point of ice
• Induces melting of ice
• Melting of ice is endothermic
• More ice melting = more endothermic reaction
• Would lower the temperature of the solution
• Lowered temperature = achieve freezing point

pH, Conductivity, and Relative Strengths of Acids and Bases

Definitions of Acids and Bases
• Arrhenius Definition
o Acid: gives off H+
§ Ex: HCl, HNO3
o Base: gives off OH-
§ Ex: NaOH, NH4OH
o However, there are compounds that are similar to properties of acids and bases that do
not have OH-
• Bronsted Lowry Definition
o Acid: proton donor
§ Ex: HCl, HNO3
o Base: proton acceptor
§ Ex: NaOH, NH3
o However, these definitions cannot explain acids and bases in inorganic compounds
• Lewis Definition
o Acid: electron acceptor
o Base: electron donor
 Properties of acids and bases
Conductivity Test

• Acids and bases have electrolytic properties = conduct electricity

• Strong acid/base = strong electrolytes = all ions dissolve
• Weak acid/base = weak electrolyte = partial dissociation

•
o Glacial acetic acid does not conduct electricity alone, but when diluted, it conducts
electricity
H+ and OH- concentration
• pH paper = pH solution
o pH < 7; acidic
§ Strong acids: 0-1
o pH = 7; neutral
o pH > 7; basic
§ strong bases: 13-14
• pH = – log [H+]
• pOH = – log [OH-]
• pH + pOH = 14

• Ampholyte: can act as both an acid and a base

pH as a function of concentration

Actual pH vs Theoretical pH
• based from pH paper
• based from concentration of H+ in the solution prepared
Relative Strengths of Acids and Bases

Relative Acidity: HCl > CH3COOH > H2CO3

Relative Basicity: NaOH > NH3
Direction of the Reaction

• Direction of reaction is determined by the relative strengths of the acids and bases.
• The more acidic/basic the reactants, the more the reaction would proceed to react the reactants
• The reaction would proceed forward