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Colligative Properties Activation Energy Concentration
Physical properties of a solution that depends on the con- Collision model Reactions occur as a result of collisions Notation Definition
centration of solutes. More solutes will lead to: between molecules. Molarity (M) (Moles solute)/(Liters solution)
Activation energy (Ea ) The minimum energy required Molality (m) (Moles solute)/(Kilogram solvent)
1. Lower vapor pressure: PA = XA PA◦ (Raoult’s for a reaction to occur. Mole fraction (X) (Moles solute)/(Moles solution)
Law) Arrhenius equation ln k = ln A − Ea /RT Mass percentage (Mass of solute)/(Mass of solution)
(This means that ln k ∝ 1/T ) Volume percentage (Volume of solute)/(Volume of solu-
2. Higher boiling point: Tb = Tb◦ + kb m (Molality) Activation energy is lowered when a catalyst is present. In- tion)
organic catalysts usually provide a site on which reactants Caution: It is an extremely common mistake to confuse
3. Lower freezing point: Tf = Tf◦ − kf m (Molality)
can adsorb; organic catalysts, or enzymes, bind specific to molarity with molality. Check your R’s and L’s!
4. Higher osmotic pressure: π = RT · M (Molarity) substrate molecules (“lock-and-key”).
Le Châtelier’s Principle
Colligative properties also depend on the van ’t Hoff factor Spectrophotometry of Concentration An equilibrium reaction will spontaneously balance an out-
(i = number of particles after reaction / number of parti- Beer’s law, A = �lc, relates concentration and light absorp- side effect added to it. For example,
cles before reaction). The greater i is, the more colligative tion. Change in amount of reactants or products: The
properties it exerts on the solution. Absorbance (A) − log10 (I/I0 ) (liquids) reaction will consume more of the substance in excess to
− ln(I/I0 ) (gases) balance the change;
Reaction Rate Absorption coefficient (�) Depends on the solution. Change in volume or pressure: The reaction will form
The reaction rate r = d[X]/dt can be determined from the Length of path (l) The length of the path travelled more gas if volume increases or if pressure decreases, and
reaction by the rate law by light. will form less gas if volume decreases or if pressure in-
Concentration (c) The concentration of the solution. creases;
r = k[A]a [B]b ... In spectrophotometry, the length of path is fixed. There- Change in temperature: Endothermic reactions will
fore, when using the same solution, A ∝ c. shift left for lower temperatures and shift right for higher
Where a, b, etc. are reaction orders for the reactants. Re- temperatures. Exothermic reactions will shift right for
action orders can only be determined experimentally, be- Gas Laws lower temperatures and shift left for higher temperatures.
cause reactions will in theory go through several steps, the STP 273 K; 1 atm
slowest of which is the rate-determining step. Reaction or- Boyle’s Law P ∝ 1/V Equilibrium Constant
der is determined by the number of atoms participating in Charles’s Law P ∝T For reactions in a solution, the equilibrium constant of a
the rate-determining step. The sum of these orders is the Avogadro’s Law P ∝n reaction
overall order. Ideal Gas Equation P V = nRT aA + bB � � sS + tT
Concentration function [X] can be determined as Law of Partial Pressure �Pn = Xn Pt Is defined as
� Effusion Rate u= � (3RT )/M [S]s [T ]t
t
Graham’s Law u1 /u2 = M2 /M1 Kc =
[X]t = rdτ + [X]0 [A]a [B]b
0 Density Formula d = (P M)/(RT )
Deviation from Ideal Behavior (P V )/(RT ) When the reaction is in equilibrium.
Therefore, for first-order reactions, Van der Waals Equation � If the reaction is a equilibrium between a solid and its ions
�
P + (n2 a)/V 2 (V − nb) = nRT in solution, then Kc is its solubility product constant, Ksp .
ln[X]t = −kt + ln[X]0 Clausius-Clapeyron Equation ln P = −∆Hvap /(RT ) + C If the reaction is a dissociative reaction of a weak acid, then
Kc is its acid dissociation constant, Ka . Polyprotic (hav-
Graphically, t is proportional to ln[X]t with the slope −k. Caution: When using the effusion rate formula, the R ing more than one H) acids have multiple Ka , but usually
And for second-order reactions, value must be in joules (8.314), and the M value must be Ka1 determines the pH.
converted to kg/mol. For a conjugate acid-base pair, Ka · Kb = Kw .
1 1 If the reactants are gases, then the equilibrium constant is
= kt + defined as
[X]t [X]0 Equilibrium Formulas P sP t
Ion-product constant of water Kp = Sa Tb
Graphically, t is proportional to 1/[X]t with the slope k. Kw = [H+ ][OH− ] = 1.0 × 10−14 (278 K) PA P B
Henderson-Hasselbalch equation When the reaction is in equilibrium.
pH = pKa + log([base]/[acid]) The Formulas above, when applied to non-equilibrium sit-
Reaction Half-time Van ’t Hoff equation d(ln K)/dT = (∆H ◦ )/(RT 2 ) uations, gives Q. The reaction forms products if Q < K,
The half-time of a reaction is the amount of time needed ln K = −∆H ◦ /(RT ) + ∆S ◦ /R reactants if Q > K, and nothing if Q = K (already in
to consume half of the reactants. It is denoted t1/2 .
equilibrium).
For first order reactions, t1/2 ≈ 0.693/k. For second order
reactions, t1/2 = 1/(k[X]0 ).
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Equilibrium Constant (cont.) Types of Magnetic Materials (cont.) Stereoisomerism (cont.)
For all equilibrium reactions, there are more reactants than Diamagnetic: Can be magnetized to repulse external E/Z isomerism: If the two ends of the bond do not have a
products if K < 1, more products than reactants if K > 1, magnetic fields, but cannot retain magnetism. Diamag- common hydrogen atom, then the compound exhibits E/Z
and the same amount of reactants and products if K = 1. netic materials have a magnetic permeability of less than isomerism. The Z isomer has the “larger” substituents
µ0 . Examples of diamagnets are bismuth and antimony. (defined by the CIP Rules) of both ends on the same side,
Acid Character of Hydrogen Atoms Ferromagnetic: Can be magnetized and retain mag- while the E isomer has the larger substituents on different
Hydrogen atoms are acidic when they are weakly bonded, netism. Ferromagnetism depends both on the chemical sides.
and when the molecule/atom they are bonded to forms composition and the structure of the material (iron is a
stable anions. ferromagnet, while stainless steel is not). Examples of fer- Cahn-Ingold-Prelog Rules
In organic compounds, the hydrogen atoms in carboxyl romagnets include cobalt and iron. The CIP Rules are used to compare two substituent groups
groups (COOH) are usually the most acidic. in the E/Z and R/S groups of naming isomers.
Nuclear Chemistry
1. Direct comparison: If the atoms that are di-
Indicators for Acid-Base Titration Alpha particles (α)
−
Helium nuclei (42 He)
rectly connected to the stereocenter are different,
Indicator Small pH Color change Large pH Beta particles (β ) Electrons (0−1 e)
Methyl violet Yellow 0.0–1.6 Violet then the atom with a higher atomic number receives
Positrons (β + ) Antielectrons (01 e) higher priority.
Bromophenol Yellow 3.0–4.6 Blue Gamma radiation (γ) High energy radiation (00 γ)
blue Units of radioactivity SI: Becquerel (Bq): 1 nucleus/s 2. Tiebreaker I: If there is a tie, then a list of atoms
Methyl orange Red 3.1–4.4 Yellow (Disintegration per second) Curie (Ci): 3.7 ×1010 nuclei/s two bonds away from the stereocenter is compiled
Methyl red Red 4.4-6.2 Yellow Units of absorbed radiation SI: Gray (Gy): 1 J/kg for each of the two substituent groups. The atoms
Litmus Red 5.0–8.0 Yellow (Energy per kilogram tissue) Rad: 0.01 Gy with the greatest atomic number from each list are
Bromothymol Yellow 6.0–7.6 Blue then compared. If they tie, then the second greatest
blue Metallurgy atoms from each list are compared. This process is
Phenolphthalein Colorless 8.3–10.0 Pink Metallurgy is the extraction of minerals from ores. repeated until the tie is broken.
Pyrometallurgy: The use of heat to convert ores to met-
Oxidation and Reduction als. (Example: Production of iron) 3. Tiebreaker II: If there is still a tie after consider
Oxidation Reduction Hydrometallurgy: The use of chemical processes in a so- atoms two bonds away from the center, then atoms
Loss of electrons Gains electrons lution to separate a metal from its ore. (Example: Bayer three bonds away are considered in the same way in
Oxidation num. increases Oxidation num. decreases process for producing aluminum) Tiebreaker I. This process is repeated until the tie is
Occurs at anode Occurs at cathode Electrometallurgy: The use of electrochemical processes broken.
Mnemonic devices: to separate a metal. (Example: Hall process for producing
aluminum) 4. Isotopes: If two groups differ only in isotopes (and
• “OIL RIG” (Oxidation Is Loss, Reduction Is Gain) are otherwise identical), then mass number is used
instead of atomic number in the process.
• “What an ox loses, a red cat gains” (An = Hydrocarbons
anode; ox = oxidation; red = reduction; cat = cath- Name Common Formula Hybridization 5. Double and triple bonds: If there is a dou-
ode) Alkane Cn H2n+2 sp3 ble bond in the substituent group, then the dou-
Cycloalkane Cn H2n sp3 ble bond is treated as a bond with “ghost atoms”
Alkene Cn H2n sp2 (e.g. R-A=B-R’ is treated as R-(A-B)-(B-A)-R’).
Electrochemical Formulas Alkyne Cn H2n−2 sp Triple bonds, similarly, have two ghost atoms for
Electromotive force E = −(∆G)/(nF ) Aromatic Cn H2n−6 sp2 each atom.
Nernst equation E = E ◦ − (RT /nF ) ln Q In a hydrocarbon with n carbons, the number of hydrogens
E = E ◦ − (0.0592/n) log Q is 2n + 2, minus 2 for each π bond or carbon ring. 6. Cycles: To handle a molecule containing one or
◦ ◦ ◦
Standard cell potential E = Ered cathode − Ered anode more cycles, one must first expand it into a tree
Energy of a charged particle E = qV Stereoisomerism (called a hierarchical digraph by the authors) by
Faraday’s Law of Electrolysis m = (Q/F )(M/z) Stereoisomerism occurs at bonds such as C=C, where both traversing bonds in all possible paths starting at
ends have two different substituents, because the rotation the stereocenter. When the traversal encounters an
Types of Magnetic Materials of these substituents are restricted. atom through which the current path has already
Paramagnetic: Can be magnetized to attract external Cis-trans isomerism: If both ends have a hydrogen passed, a ghost atom is generated in order to keep
magnetic fields, but cannot retain magnetism. Param- atom substituent, then the compound exhibits cis-trans the tree finite.
agnetic materials have a magnetic permeability of more isomerism. The cis-isomer has both hydrogen atoms on the
than µ0 . They usually have free electrons, especially d same side, and the trans-isomer has the hydrogen atoms
and f electrons. Their magnetization follows Curie’s Law on different sides.
(M = C · B/T ). Examples of paramagnets are tungsten
and cesium.
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Criteria of Aromaticity Functional Groups (cont.) Enantiomerism
If a hydrocarbon Functional Group Name Suffix/Prefix System Name Based On
R-CH2 C6 H5 (benzyl, toluene der. benzyl- R/S Structure
1. Is cyclic, i.e. possesses a carbon ring; Bn) (+)/(−) Direction of rotation of polarized
R-C5 H4 N (pyridyl) pyridine der. pyridin-x-yl light
2. Is planar, i.e. all carbons on the ring are on the same D/L Enantiomer of glyceraldehyde the
plane; Note: In actual compounds, change all instances of “halo”
above to halogen names (fluoro, chloro, bromo, iodo). molecule is derived from
R/S notation: Orient the enantiomer so that the small-
3. Has an uninterrupted cloud of π electrons;
est (by CIP Rules) substituent points backward (away from
Amino Acids the viewer) and the largest substituent points upward. If
4. The number of pairs of π electrons in the cloud is Hydrophobic amino acids:
an odd number, i.e. the number of π electrons in the Name Code Name Code the larger substituent of the other two points toward the
cloud is 4n + 2; right, then the enantiomer is an R-enantiomer. If the larger
Alanine Ala Valine Val
substituent points toward the left, then the enantiomer is
Phenylalanine Phe Methionine Met
then the hydrocarbon is aromatic. Aromatic compounds an L-enantiomer.
Leucine Leu Proline Pro
are highly stable (cannot undergo addition reactions), but (+)/(−) notation: An enantiomer that rotates the plane
Isoleucine Ile Tryptophane Trp
can undergo substitution reactions. of polarization clockwise is dextrorotary (+). An enan-
Hydrophilic amino acids: tiomer that rotates the plane of polarization counterclock-
Functional Groups Name Code Name Code wise is levorotary (−).
Functional Group Name Suffix/Prefix Glycine Gly Threonine Thr D/L notation: An enantiomer that is derived from (+)-
R-OH (hydroxyl) alcohol -ol Serine Ser Cysteine Cys glyceraldehyde is the D-enantiomer. An enantiomer that
R-O-R’ (ether) ether ether Tyrosine Tyr Asparagine Asn is derived from (−)-glyceraldehyde is the L-enantiomer.
R-X (halo) haloalkane halo- Glutamine Gln Arginine Arg Note that nomenclature in a system cannot be determined
R-NH2 (amino) amine -amine Lysine Lys Histidine His by that in another system.
R-COH (aldehyde) aldehyde -al Aspartic acid Asp Glutamic acid Glu Caution: The (+)/(−) system is sometimes written as
R-COX (haloformyl) acyl halide -oyl halide (d)/(l), which is easily confused with the D, L system. As
R-CO-R’ (carbonyl) ketone -one Protein Structure these two systems sometimes conflict (a D-enantiomer can
R-COOH (carboxyl) carboxylic acid -oic acid Proteins are large biochemical complexes that contain sev- be an (l)-enantiomer), the (+)/(−) notations are strongly
R-COO( carboxylate) carboxylate -oate eral polypeptide compounds (amino acid chains). They preferred.
R-COO-R’ (ester) ester -oate are organized into four levels of structure:
R-CONH2 (amide) amide -amide Primary structure: The chain of amino acids that make Significant Figures
R-CNH-R’ (ketimine) ketimine imino- up the protein; this chain directly controls the other levels Significant figures (“sig figs”) is the number of digits that
R-CHNH (aldimine) aldimine imino- of protein structure. carry precision in a number.
R-CONCO-R’ imide imido- Secondary structure: The patterns formed by segments Non-measured Numbers: Non-measured numbers,
(imide) of the polypeptide chain; can be either α-helices or β- such as π, integer counts, definition of units, etc. always
R-N3 (azide) azide azido- pleated sheets. have infinite sig figs. Other constants, such as NA , have
R-N2 -R’ (azo) azo azo- Tertiary structure: The folding of the polypeptide to limited sig figs.
R-OCN (cyanate) cyanate cyanato- produce a certain shape. Non-zero Digits: Nonzero digits are always significant,
R-NCO (isocyanate) isocyanate isocyanato- Quarternary structure: The geometrical bonding of unless one or more of the other rules are violated.
R-CN (nitrile) nitrile cyano- several polypeptides to form the protein. Zeros: Leading zeros are never significant; trailing zeros,
R-NC (isonitrile) isonitrile isocyano- however, are significant only if they are part of the mea-
R-NO (nitroso) nitroso nitroso- Chirality surement. Zeros between non-zero digits are always signif-
R-NO2 (nitro) nitro nitro-A molecule possessing a nonsuperimposable mirror image icant.
R-ONO (nitrosooxy) nitrite nitrosooxy- is chiral. Reporting Numbers: Reported numbers are only signif-
R-ONO2 (nitrate) nitrate nitroxy- Two mirror images of a chiral molecule are enantiomers. icant to the precision of the equipments with which they
R-SH (sulfhydryl) thiol -thiolA carbon that is bonded to 4 different groups is an asym- are measured.
R-SCN (thiocyanate) thiocyanate thiocyanato- metric center. Chiral molecules have at least one asym- Addition/Subtraction: When adding or subtracting
R-NCS (isothio- isothiocyanate isothiocyanato- metric centers. two numbers, the result should have as many decimal
cyanate) Chiral molecules rotate polarized light. Two enantiomers places as the number with the smallest sig figs.
R-CSH (carbonoth- thial -thial rotate polarized light by the same degrees, one clockwise Multiplication/Division: When multiplying or divid-
ioyl) and one counterclockwise. A mixture of two enantiomers ing, the result should have as many sig figs as the number
R-PH3 (phosphino) phosphine -phosphane in 1:1 does not rotate polarized light, and is racemic. with the smallest sig figs.
R-C6 H5 (phenyl, Ph) benzene der. phenyl-
c
�2009–2011 Zee Zuo. Licensed under CC-BY-SA 3.0, United States. Revision 3
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