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Reactions of Alcohols:
What are the two forms of reaction? |
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Definition
| Oxidation and Dehydration |
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Term
Reactions of Alcohols:
_____ alcohols require two oxidation steps. The first step produces a(n) ________, and the second step produces a symmetrical ________. |
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Definition
1* (primary)
aldehyde (R-CHO)
carboxylic acid (R-COOH) |
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Term
Reactions of Alcohols:
____ alcohols only require one oxidation step, which produces a ______. |
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Definition
2* (secondary)
ketone (R-COR) |
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Term
Reactions of Alcohols:
In the first/only step of oxidation, where is each of the two hydrogen protons removed from, respectively?
What functional group results from this removal? |
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Definition
one from the hydroxyl (-OH), the other from the containing carbon
result, carbonyl group (C=O) |
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Term
Reactions of Alcohols:
In an oxidation reaction, what exactly is being oxidized? |
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Definition
| usually, the metal ion of the oxidizing agent, such as the Cr (which oxidizes from 2+ to 3+) in K2Cr4O7 (potassium dichromate) |
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Term
Reactions of Alcohols:
Can ketones be further oxidized? |
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Definition
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Reactions of Alcohols:
After the oxidation reaction of an alcohol, what reagent is administered to the product, under what conditions, to determine the whether the product is either an aldehyde or a ketone?
The presence of a(n) ____ ion in the product indicates the formation of a(n) ________. |
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Definition
diamminesilver (I) complex, in basic conditions
Silver (Ag), aldehyde |
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Term
Reactions of Alcohols:
What are the two classifications of dehydration reactions? |
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Definition
| intra- and intermolecular |
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Term
Reactions of Alcohols:
Intramolecular dehydration in an alkane chain containing a ___ alcohol (unless it is 2-propanol) will normally yield a major and a minor product. According to Saytev's Rule, which would be the major product? |
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Definition
secondary
Saytev's Rule-- On a chain, if the hydroxyl-carrying carbon is sandwiched between two carbons, the hydrogen will be taken from the carbon with the least number of attached hydrogens, as this carbon theoretically should have a weaker hold on its bonded hydrogens. |
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Term
Reactions of Alcohols:
The product of intermolecular dehydration is a(n) _____. |
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Definition
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Reactions of Alcohols:
Intermolecular dehydration is only effective for ___ alcohols, and produces a(n) _____. |
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Definition
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Definition
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| which acids always go by their common name? |
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| ________ reactions are characteristic of ________ compounds such as _______, _____ _______, and ________ _________. |
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Definition
Substitution
saturated
alkanes, alkyl halides, and aromatic compounds |
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Term
| ________ reactions are typical of compounds containing multiple bonds. For example, ethene reacts with Br2 by breaking its pi bond to add both Br atoms to its molecule. Both reactants become a product. |
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Definition
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| ___________ reactions work counter to addition reactions. They create molecules such as ethene. |
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| In a ______________ reaction, molecules undergo a reorganization of their substituent parts. |
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Definition
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Definition
The breaking of a bond producing two identically charged particles; each parting atom takes with it one pair electron
these particles are called "radicals" |
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Definition
| the splitting of a bond resulting in a conjugate acid (+) and a conjugate base (-) |
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| Bronsted-Lowry definition of acids and bases |
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Definition
acids are the reactants which will donate a proton;
bases are the proton acceptors |
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Definition
| acids (electrophiles) will accept an electron-pair from the base (nucleophiles, or electron-pair donor |
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Definition
:Y + A:B -> Y:A + B:
where Y is the molecule which gives an electron pair to A, which furnishes the energy to break the bond between A and B |
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diprotic acids
at what percent does the second proton react? |
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Definition
can donate two protons (i.e. H2SO4)
10%, due to the leveling effect of water |
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Definition
| water equilibrates its molecules by proton transfer so that no base present is stronger than -OH |
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Definition
| hydrogen-bonding around oppositely-charged ions (like NaCl) causes them break apart in water |
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| in a reaction between HCl and NaOH, what are the spectator ions? |
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Definition
ions which do not take part in the reaction
Na and Cl |
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Definition
| the net reaction between all strong acids and bases |
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Term
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Definition
| proton transfer reactions starting (acid and base) and ending (conj. acid and conj. base) in two reactants and products |
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Definition
| ion with a positively charged carbon |
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Definition
| ion with a negatively charged carbon |
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large value of K(a)
small value of K(a) |
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| the concentration of water |
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| How do we compare the strengths of the conjugate acids/ conjugate bases of two compounds? |
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Definition
| compare the effects of their reaction with water. |
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Definition
| acid-base reactions favor the formation of the weaker acid and weaker base |
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Term
| Carboxylic acids containing more than 5 atoms are water insoluble, unless a chemist does THIS. |
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Definition
| Higher carb acids react with sodium hydroxide to create water soluble salts |
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Term
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Definition
| if a polar substituent is attached to a nonpolar carbon chain, the inductive effect will attract electrons to the substituent. With increase in distance from the substituent, the inductive effect weakens. |
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Term
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Definition
| more s-character, higher Ka value, greater acidity |
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Definition
down the periodic table, acidity increases
across row, acidity increases |
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Definition
change in enthalpy with the standard conditions
enthalpy is associated with changed in bonding. If a high order bond becomes a low order bond, enthalpy is positive (endothermic, to break bonds).
If two weak bonds become two strong bonds, then enthalpy is negative (exothermic)
if H is negative, G will become more negative |
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| Gibbs free energy, relationship to H and S |
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Definition
| (delts)G = (Delta)H - T(delta) S |
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| gibbs free energy, relationship to Keq |
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Definition
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Definition
| changes in the relative order of a system |
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| entropy and the relative order of a system |
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| the more random a system, the greater the entropy |
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Term
positive, negative, or zero?
entropy changes associated with:
A + B --> C
A + B --> C + D
A --> B + C |
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Definition
(-)S : state of disorder to a state of order
(0)S: no change in order
(+)S: Order to disorder |
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Term
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Definition
RCOOH
do not give up a proton unless in the presence of an alcohol, which has a pKa of 15-18 |
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Term
at which phase are acids the weakest?
what is solvation and how does it help? |
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Definition
gas phase
no solvent can contribute hydrogen bonding or ion-dipole interactions to stabilize the acid |
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Term
| internal structural and electronic features |
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Definition
| for acids in the gas phase lacking solvation to stabilize their ions, this determines gaseous acid strength |
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| effect of solvation on entropy |
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Definition
| solvation of an acid increases order, and decreases entropy |
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Term
| Free energy of strong acids |
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Definition
| strong acids have a low free energy value, and are ordered |
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Term
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Definition
| a solvent that binds to its solute by hydrogen-bonding |
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Definition
| is the conjugated acid of an alcohol |
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Definition
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Definition
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| proton transfer reactions are... |
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Definition
| ... the first step in alcohols, esters, ethers, carboxylic acid, and ketone reactions |
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Term
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Definition
they are unstable intermediates formed during reactions where a pi-bond is broken in an alkene and a sigma bond is broken in an acid ( H:A ), so that the then-alkene-now-alkane can accept the H-proton from the :A- conjugate base.
carbocations are unstable and usually undergo two interactions |
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