EXAMKRACKERS AUDIO OSMOSIS ORGANIC CHEMISTRY

Lewis Dot Structures

o Count total number of valence e for all
o Two electrons/bond
o Arrange remaining around atoms to satisfy around octet rule
Breaking octet rule:
o Atoms with more than octet of electrons must come from third period on periodic table since vacant d orbitals
are required
o Sulfur, phosphorus
o Boron, beryllium may contain less than an octet
Valence = number of bonds an atom normally makes
o Carbon = tetravalent
o Nitrogen=trivalent
o Oxygen = divalent
o Halogens = monovalent
Formal charge: number of electrons on neutral atom minus how many electrons that atom has in the Lewis structure
Fischer projection: vertical lines are directed into plane of the page.
Dashed lines go into page. Solid wedges come out of the page
Newman projection: staring down length of bond typically between 2 carbons
Amides: carbonyl compound
o Bonded to a nitrogen
Amine: nitrogen bonded to carbons and/or nitrogens
Gem-dihalide: a ccompound with 2 halogens attached to the same carbon
Single halogens attached to adjacent carbons: vic-dihalide
Alcohol that has donated a proton: alkoxide ion
Carbon triple bonded to nitrogen: nitrile
Carbon-carbon double bond attached to something else: vinyl
NO = nitroso
NO2 = nitro
Meth, eth, prop, but, pent, hex, hept, oct, non, dec
N-propyl and n-butyl are just NORMAL straight chains with 3/4 carbons
Sec-butyl and tert-butyl and both refer to first carbon on chain
o Sec stands for secondary, as in the first carbon on the chain is secondary!!
o Tert stands for tertiary, meaning attached to 3 other carbons
Isobutyl: shaped like a T with first carbona s primary
Isopropyl: shaped like a T with first carbon as secondary
To name, look for longest carbon chain with most substituents
Carbon with double or triple bonds should get lowest number possible
Order substituents alphabetically ignoring number prefixes
Electrons are at their lowest energy level when they are closest to the nuclei
Bond is formed when a pair of electrons can lower their energy by positioning themselves between the two nuclei
Sigma bond: electrons spend the msot time between the nuclei
Pi bond: electrons must occupy space above and beyond sigma bond because there is no room between the nuclei!!
Sulfur> phosphorus> and silicon are highly unlikely to form double and triple bonds in this order!
Electrons in pi bond must have higher energy than sigma electrons
Pi bond is more reactive than sigma bon
Overall bond length of a double bond is shorter than a single bond and bond strentth is greater
Bond strength and length are inversely related
 Orbital in s subshell has lower energy than orbital in p subshell
Neutral carbon has 4 valance electrons: 2 in s subshell and 1 in p subshell
o Higher energy p orbitals combine with lower energy s orbitals combine to form a molecular orbital between
the two
o Hybridized orbitals on oxygen in water: sp3
o Hydrogens in water: s because hydrogen has only 1 valence electron
o Carbon in 2 single bonds and 1 double bond: sp2
Sp2 = 120 degrees
Sp3 = 109.5 degrees
Lone pairs and ring structures can deform angles slightly
Water bonds: 104.5 degree angles instead of 109.5 expected angle
Sp = linear
Sp2 = trigonal planar
Sp3 = tetrahedral,pyramidal, or bent
o Sp3 of ammonia = pyramidal
o Sp3 of methane = tetrahedral
Resonance: occurs with delocalized electrons
Molecule does not resonate back and foth
o Weighted average of resonance structures
o Actual benzene has no double bonds, but they are partial double bonded in character as in the single bonds are
shorter and stronger in character but still considered single bonds
o Resonance stabilizes a molecule
Actual molecule is most stable than any of the resonance structures
4 rules for resonance
o Atoms must not be moved, only electrons
o Number of unpaired ele ctrons must remain constant
o Resonance atoms must lie ins ame geometric plane. This is why benzene is a flat molecule
o Only proper lewis structures can be resonance structures
Ring structures must satisfy Huckels rule!! ONLY RING STRUCTURES!
Even though most molecules are neutral, they can have separation of charge
o Center of charge of negatively charged electrons may not COINCIDE with center of charge of positively
charged nuclei
o A dipole moment is created when this happens
Dipole moment is pointing fromn center of positive to center of negative charge
o Mu = d between centers of charge*total charge q of either center NOT CHARGE OF BOTH CENTERS!
Strongest kind of dipole-dipole force is hydrogen bond
o Hydrogen bonds are still far WEAKER bonds
o Dipole moment is a vector
o Dipole moments of bond may add up to 0 and thus cancel. Thus a molecule with polar bonds (dipole
moments) may not be polar overall
Momentary dipoles: only forces that cause nonpolar molecules to be attracted to one another
o London Dispersion forces
o Van der Waals forces
This may also refer to ALL types of dipole forces
Must look at context in which it is used
Iso: same
Isomers have same molecular formula but are not same compound
Newman projection with anti, gauche, eclipsed:
o Anti has two largest groups as far as possible as possible
o Gauche: groups exactly opposite are NOT the biggest groups
Different compounds with same molecular formula are isomers
If isomers have different bond-bond connections, they are structural isomers:
 o Two dichlorobutanes but one has both halogens attached to first carbon whereas the other has one attached to
each carbon
o Obviously, same molecular formula but different connections
o Have different molecular and physical properties
Chirality: almost always have 4 different substituents attached
Absolute configurations:
o Number substituents from highest to lowest priority based upon atomic weight.
o Counterclockwise: S
o Clockwise: R
o If one carbon is double bonded to an oxygen, it is considered to be bonded to two oxygens for the purpose of
priority assignment
Relative configuration requires comparison of 2 chiral molecules
o If they have same relative configuration, it means similar substituents are in same place in terms of their
chiral centers
o Relevant in terms of sn1 and sn2 reactions in which half of the configurations are retained and completely
inverted, respectively
Chiral compounds rotate plane polarized light
o When photon strikes a molecule, it refracts, rotating the electric field
o When same photon strikes mirror image, it rotates back exactly the same distance
o Mirror image cancels out the rotation
o Achiral molecules are their own mirror image, and thus mirror images cannot be separated from compound,
so these never have opportunity to rotate plane-polarized light
o Enantiomers rotate in same degree but in same directions
o Clockwise: d/+
o Counterclockwise/- both of tehse l/- are called observed rotation
o Specific rotation: observed rotation with parameters, such as concentration, etc
Light is an electromagnetic wave where each photon creates an electric field and a magnetic field perpendicular to
each other and to direction of photon movement.
Enantiomers and diastereomers are the two types of stereoisomers
Enantiomers have SAME physical & chemical properties except way they rotate plane polarized light and the way
they react to other chiral compounds
Racemic mixture: mixture of enantiomers
Resolution: separating a racemic mixtures
Cis/trans isomers are diastereomers. Occurs when two atoms are connected by a bond that cannot rotate about its axis
and 2 carbons have an identical substituent
Cis isomers have dipole moments: HIGHER BOILING POINTS, HIGHER HEATS OF COMBUSTION
Trans isomers: more symmetrical AND TEND TO HAVE HIGH MELTING POINTS!
E = HIGHEST PRIORITY ATOMS ARE ON DIFFERENT SIDES!
Z= HIGHEST PRIORITY ATOMS ARE ON SAME SIDE
In labeling E/Z, divide the double bond vertically and label and then compare the highest priority groups of each one
horizontally
Meso compounds: more than one chiral carbon and an internal plane of symmetry
o Cannot have enantiomers
Methyl carbon is attached to 3 hydrogens
Physical properties of alkanes
o The more carbons, the higher the melting/boiling point
o True waxes are ether
o Branching increases the melting point, but decrease the boiling point
This is because breanching chains are more compact, which weakens van der Waals forces and lowers
the boiling point while same compound structure allows same alkane to pack easily and form a solid
o Alkanes are less dense than water. Specific gravity = 0.7. insoluble in water. Think of oil spill
o When alkane is attached to polar group, the polarity and solubility go down!
 Ring strain is 0 for cyclohexane
Effects of ring strain can be seen using a bomb calorimeter. With ring strain, will exhibit a high heat of combustion
per CH2 group when placed here.
Ring strain gives molecule higher energy/CH2 group
Cyclohexane:
o Exists as several conformers: same molecular formula and connectivity,b ut different orientation
o Conformers are chair, half chair, twist, and boat
o Important ones to know are chair and boat
o Twist is lower in energy than boat
o Boat is in higher energy than chair conformation
o For hydrogen, neither axial/equatorial is favored from an energy position
Alkanes are not very reactive
o Do not react with strong acids/bases
o If add enough energy, they will react violently with oxygen
Combustion: a reaction with oxygen
Energy of activation of combustion with alkanes is very high, but once the reaction begins, the reaction is exothermic
enough to be self-perpetuating
o Products are water and carbon dioxide
o Radical reaction
o Exothermic, high activation energy
I2 does not typically react with alkanes to form alkyl halides
Halogenation requires heat or light to initiate reaction
o Chain reaction
Halogen molecule alone will not react with alkane. Halogen ishomolytically cleaved .this creates 2
radicals
The unpaired radical is neutral but is highly reactive and is very unstable
Never exists in high concentration
Radical reaction: initiation, propagation, termination
o Net reaction is sum of initiation and propagation
1 halogen + 1 alkane = 1 alkyl halide + 1 hydrogen halide
o Termination steps are important when there are few reactants available
o Usually results in mixed products, like multi halogenated alkyol halides and alkyl halides halogenated at
different carbons
o Exothermic
o Reactivity of alkyl radicals is same as reactivity of carbocations. Methyl are most reactive
o Iodine is least reactive halogen, and most selective
o Bromine prefers to add tertiary while fluorine reacts with any primary or secondary or tertiary.
Alkenes:
o Pi bond occupies space above and below sigma bond
o Inductively electron-withdrawing
o Greater molecular weight, higher the boiling point, and density. Slightly more soluble in water than alknes
not very soluble in water
o Typically float on water as they are less dense
o Easily dissolve in solvents with low polarity
Synthesizing alkenes
o Via elimination reaction
o E1 or E2 mechanism
o E1 occurs in two steps and E2 occurs in one step
E2 reaction:
o E2 dehydrohalogenation
o Strong bulky base is added to alkyl halide
Base is too bulky to act as nucleophile
 As a base, it must accept a proton
Dehydration of alcohol
o E1 reaction
o *IMPORTANT
o Add a hot, concentrated acid to an alcohol
o Has a carbocation intermediate
o Leaves an alkene
o Acid is actually a catalyst here
o Major product is most substituted alkene
Catalytic hydrogenation
o Two hydrogens are addedone to each carbon in double bond
o SYN additionhydrogens add to same side of alkene
o Erythro: similar functional groups are on same side in a fischer projection
o Threo: func gropus on different sides on Fischer project
o Catalyst is heterogeneous
o Exothermic reaction
o CATALYST DOES NOT CHANGE THERMODYNAMICS OFA REACTION(ENDO/EXO)
o Hydrogenation of an alkyne makes an alkene
Oxidation of an alkene:
o Adding ozone (O3) which is high energy
o Cleaves through double bond leaving 2 separate molecules with carbonyl groups
o Permanganate with HEAT also splits alkene in two
If aldehydes is formed, it is oxidized to carboxylic acid
*Without heat, permanganate followed by a base makes a glycol in hydroxylation
o Glycol: diol
o OsO4 also produces a glycol when added to alkene
Electrophilic addition:
o Electrophile will usually have a positive or partial positive charge
o Add to alknees by attacking pi bond electron cloud
o Add via Markovnikovs rule:
Electrophiles (hydrogen ions) add to elast substituted carbon of alkene; this is because it forms the
most stable carbocation!!
o Whenever a carbocation is formed, a skeleton rearrangement may occur
Peroxides: HBr will add anti-markovnikov where hydrogen adds to most substituted carbon
o Radical reaction where bromine radical adds before the hydrogen
o Occurs with HBr, not HCl, not HI, not HF
Adding water to an alkene:
o Reversing dehydration of an alcohol
o Cold, dilute acid cause addition of water to an alkene
Electrophilic addition
o Carbocation is formed, hydroxyl group is added, and alcohol is formed
o MARKOVNIKOV ADDITION
Rearrangement must be possible
Oxymercuration
o Prevents carbon-skeletal rearrangement during hydration
o Organiometallic compound bonds to both double-bonded carbons
o Water attacks from opposite side in an anti addition
o Forms an alcohol
o Alcohol may also be used as the solvent in this reaction
Hydrating alkene with anti Markovnikov addition
o HydroborationBH3 and then peroxides
o REMEMBER PEROXIDES CAUSE ANTI-MARKOVNIKOV
 Halogenation of an alkene
o Electrophilic
o As they are more reactive, alkenes do not need to create a readical in order to make them react with halogen
o Anti addition
o One halogen adds to each, but on opposite sides
Benzene is a flat, six-carbon ring
o Bonds have only partial double-bond character as pi electrons are delocalized around the ring
o Undergoes electrophilic substitution, not addition
Addition would destroy its resonance, leading to a more unstable molecule, and such reactions are
unlikely to occur
o Ortho, on either side directly
o Meta, two carbons away
o Para, directly across the ring from the substituent
o **If substituent is electron-withdrawing, it deactivates and directs next substituent to add at meta position
Oxygens withdraw electrons via double bonds
Nitrogens with 4 bonds, they withdraw electrons
Halogens are actually electron withdrawing, but NOT meta directed
Carbonyls, nitriles (Cyanide)
o If it is electron-donating, it activates ring, and directs to add ortho or para
Halogens are the exception here!
Oxygens donate electrons via single bonds
Nitrogens with only 3 bonds donate electrons
Alkyl groups are electron donating
Benzene
SN1:
o Occurs in 2 steps
o First step is the slow step
o Usually alkyl halide is tertiary, for no backside attack
o Halogen acts as the leaving group, and a small nucleophile bonds to the carbocation
o Rate depends solely on the concentration of the substratealkyl halide
o Carbocation flattens out, and nucleophile can add to either side
o If it were chiral, product would be a racemic mixture**
o Works best in polar solvents which would STABILIZE THE CARBOCATION
o Does not occur often with secondary
Carbocations are too unstable
o Skeletal carbocation rearrangement is possible
o Sn1 and E1 usually occur together to form mixed products
Sn2:
o Occurs in 1 step
o Alkyl group is NOT bulky
o Nucleophile is a non-bulky strong base
o Halogen is dislodged after the nucleophile comes in
o Inversion of relative configuration occurs
o Rate depends upon nucleophile, and the substrate
o Requires primary, secondary carbon as substrate
o If base is too strong, and substrate/base is sterically hindred, an e2 reaction will occur
Nucleophilicity:
o Base bonds to a proton and a nucleophile bonds to a carbon
o Good base is often a good nucleophile
Base is always a better nucleophile than its conjugate acid
o Less bulkiness in the base ---nucleophile
o Negative charge&polarizabilitynucleophile
 o Electronegativitiyreduces nucleophilicity
o Nucleophilicity increases going down and to the left on the periodic table
Nucleophile and 5 Ss:
o Sn2 requires strong nucleophile whereas it is unimportant in sn1
o Substratetertiary = sn1, and rest = sn2
o Solventpolar solvent increase rate of sn1 by stabilizing carbocation but inhibit sn2 by stabilizing
nucleophile
o Speedsn2 depends on nucleophile and substrate, whereas sn1 depends only on substrate
o Stereochemistrysn1 = racemic and sn2 = inversion
o Skeletonin sn2, no carbocation rearrangement, as there is no carbocation!!
Alcohol: organic compounds containing a hydroxyl group. CO bond is longer than OH bond. Bond angle is closer to
109.5 degree angle due to bulk of alkyl group. Lower molecular weight alcohols are miscible with water because
alcohol can hydrogen bond and are also less dense than water. Boiling points decrease with branching.
Alcohols are very weak acidsweaker than water in most cases.
Primary alcohols are most acidic followed by secondary then tertiary.
Alkyl group in alcohol is electron donating
Phenol is benzene with a hydroxyl group.
Conjugate base of alcohol: alkoxide ion
We can synthesize alcohol by adding Grignard reagent to a carbonyl group. Grignard is organometallic compound.
Metal has a partial positive charge because metals like to lose electrons leaving alkyl group with negatively charged
carbon. Negative charge thus makes a nice nucleophile. Grignard is nucleophile attacking carbonyl carbon. Oxygen is
protonated in an acid bath afterwards.
Reduce ketone/aldehydes to make alcohol via: NaBH4 and LiAlH4. These two are salts that make ions when placed in
water. Both are eager to donate a hydride ion (H-). Acid bath protonates oxygen afterwards
o NaBH4 only reduces to primary and secondary alcohols.
o LiAlH4 will reduce esters and acetates to alcohol as well. Thus, stronger reducing reagent.
Alcohol can be oxidized to make ketone, aldehydes, or carboxylic acid. Primary oxidizes to aldehydes or carboxylic
acid. Secondary oxidizes to ketone. Hydroxyl group by itself is a terrible leaving group.
If we add acid halide to alcohol, it protonates hydroxyl group and halide acts as nucleophile.
o Use SOCl2 as halide
Ether: polar aprotic solvent with low reactivity and dissolves a wide range of solvents without reacting. When adding
hydrogen halide, ether is split.
Epoxide: reactive ether in a ring similar to a triangle. Reactive because it has much angle strain.
Order of acidity: weakest to strongest: alkane, alkene, H2, NH3, alkyne, aldehydes, alcohol, water, carboxylic acid
Carbonyls: pi electrons are pulled towards oxygen. Oxygen might even accept one pair of the electrons and take on a
negative charge. Carbonyl carbon has a partial positive charge. Carbonyl carbon makes 3 sigma bonds and is sp2
hybridized. Compound is flat at carbonyl carbon.
Aldehydes: similar chemistry to ketones. Simplest one is formaldehyde (methanol??). Simplest ketone is acetone or 2-
propanone. Higher boiling points than similar weight ethers but lower boiling points than alcohols. Good solvents for
alcohols and means short chain aldehydes/ketones are soluble in water.
Aldehydes and ketones are susceptible to Nucleophilic attack. Like to undergo Nucleophilic addition because they
dont have good leaving groups. May also behave as a Bronsted-Lowry acid. They donate the alpha hydrogen.
When conjugate base is stabilized, acid gets stronger.
Oxygen in carbonyl is willing to take on an electron from the carbonyl bond. Stabilized by resonance
Aldehydes and ketones are weaker acids than alcohol
Tautomers: structural isomers where a proton has shifted. Exist in equilibrium. These are NOT resonance structures.
Tautomerizatoin is reaction with equilibrium favoring aldehydes/ketone.
Aldehydes/ketone in alcohol: intermediate compound is hemiacetal or hemiketal. Catalyzed by acid or base. Can take
it one step further by adding another equivalent of alcohol to form an acetal or ketal. Can only be catalyzed by acid,
not base, because acid creates water as the leaving group. We can reverse this reaction just by adding acid!
Germinal diol: carbonyl carbon has oxygen replaced by two hydroxyl groups
 Aldol condensation: aldehydes/ketone reacts with itself and behaves both as acid and as Nucleophilic addition
substrate. Can be catalyzed by acid/base. Alpha hydrogen is removed forming negatively charged alpha carbon on
enolate ion and this attacks carbonyl on other aldehydes/ketone. Aldol is then formed in the end. This much is called
aldol addition. The condensation part, a second alpha hydrogen is removed with hydroxyl group.
Conjugation: double bonds separated by just one single bond. More stable than isolated double bond systems. A
double bond between alpha and beta carbon of carbonyl is conjugated. Here, electrophile may add to carbonyl
oxygen. Following with nucleophile, that adds to beta carbon.
Carboxylic acids: common names: formic, acetic, and benzoic acid.
o Strong organic acids but weak compared to strong inorganic acids. Weaker than hydronium ion, for instance.
o Spreading negative charge over a larger area always stabilizes. Follow same melting/boiling point trends as
hydrocarbons with much higher melting and boiling points due to hydrogen bonding. Chains with 8 or more
carbons are generally solid.
Carboxylic acids like to undergo Nucleophilic substitution. True for derivates of these as well.
Add PCl3, PCl5, or SOCl2 to carboxylic acid: get Nucleophilic substitution. Acid chloride is left behind. Called an
acyl chloride and donates an alpha hydrogen. Acid chloride is more acidic than an aldehyde.
o Chloride ion is a good leaving group
o Alcohol+ acid chloride = ester
o Carboxylate + acid chloride = anhydride
Amines: ammonia derivatives with one or more alkyl or aryl groups bound to hydrogen. Ammonia, primary and
secondary amines form hydrogen bonds. Hydrogen bonds formed by amines are not as strong as those formed by
alcohols. Act as nucleophile or as lewis base. Electron donating groups strengthen basicity of amines. Nitrogen is
willing to make a fourth bond by taking on a positive charge.
o Like to be nucleophiles
o Add to carbonyl carbon in presence of an acid
o Amine attacks carbonyl carbon but final result is complete replacement of carbonyl oxygen with nitrogen.
Product is called an imine.
o Amine can react with any of carboxylic acid derivatives to create an amide which is an amine attached to a
carbonyl.
o Acid chlorides are most reactive then followed by anhydride then ester then amide. Amide is most stable of
them all. Alkyl halide will react with ammonia to make primary amine.
Nitriles: carbon is partially positive. Can be hydrolyzed in acid to give a carboxylic acid. Can be reduced to give
amines.
Fatty acids: long chained carboxylic acids.
Be able to draw structure of an amino acid.
Alpha amino acids are used to make proteins. Nearly all organisms use same 20 alpha amino acids.
o 10 of common amino acids are essential to humans
Two amino acids attached by one peptide bond = dipeptide
Isoelectric point of amino acid: when amino acid starts with negatively charged carboxylic acid and positive amine=
zwitterions. Four characteristics dipolar creates: high melting point, water solubility,, large dipole moments, and
makes amino acid less acidic than most carboxylic aids but less basic than most amines. Isoelectric point is pH at
which this amino acid exists as a zwitterion
Carbohydrates are a one to one ratio of carbon to hydrogen. Glucose is a hexose. Makes glycogen, starch, cellulose,
and chitin. Plants store glucose as starch. Plant cell walls are made of cellulose. Beta linkages in cellulose and chitin.
Alpha linkages in others. Humans absorb only D glucose.
NMR: proton-NMR, usually on the MCAT. Uses constant frequency photon source and changes magnetic field til
resonance is detected. If no electrons around nucleus, all protons would exhibit resonance at same field strength.
Protons shielded from external mag. Field by electrons require a stronger external magnetic field to exhibit resonance
o Electron withdrawing groups deshield protons allowing them to resonate at lower field strength. Numbers
increase to the left. Larger numbers indicate a weaker magnetic field strength. To left is called downfield.
Carbonyl proton has peak at around 9.5 ppm. IMPORTANT!!
o Spin-spin splitting: occurs when neighboring hydrogens that are stereochemically different from each other.
 such hydrogens are enantiotropic to each other. Each peak splits in same number of peaks as non
enantiotropic neighbors plus 1!
Group of peaks with more hydrogens has greater total area under the peak. Horizontal line called integral trace can be
drawn at spectrum and will rise and stay at new height each time it reaches top of new peak and extent it rises is
proportional to this amount of hydrogen. A rise of 2 represents twice as many hydrogens as a rise of 1.
IR spectroscopy: infrared. Perpendicularly oriented constantly changing magnetic field.
o Elastic component tends to increase frequency.
o Carbonyls register strongly. Deep sharp dip at 1700 cm^-1 which is unit called wavenumber. Number of
waves in each centimeter. Alcohols are at 3200-3600 with very broad peaks. Fingerprint region: each
compound has unique IR spectrum which is between 600-1400. No polar bonds make weaker signals.
Chromatography: resolution of a mixture by passing it over a surface that adsorbs compound in mixture at different
rates. Moving phase and stationary phase. Stationary phase is the surface and moving is some type of solution. As
moving phase moves over stationary, compounds with greater affinity for stationary move more slowly. More polar
have greater affinity for stationary phase. In column chromatography, solution with mixture is dripped down a column
of glass beads.
Paper chromatographyknow it!
Thin layer chromatography
Gas chromatography: mixture dissolved in heated carrier gas. Results recorded as peaks.
Distillation: separation based upon boiling points. Unless azeotrope, boiling point of mixture is same as boiling point
of compound in mixture with lowest boiling point. Poured into condensing flask. Should be done slowly!
Crystallization: crystals tend to form from pure substances. Mixture to be purified is melted and crystallized many
times
Extraction: based upon solubilities. Nonpolar layer and aqueous layer. Nonpolar layer usually contains mixture. Acid
is added and apparatus with both layers is shaken vigorously. Acid protonates mixture in nonpolar mixture. Protonated
bases settle out in aqueous which is drawn off. Next, weak base is added and shaken. Weak base Deprotonates strong
acids which settle in aqueous and are drawn off. Strong base is added and apparatus is shaken. Deprotonates weak
acids which then also settle out in aqueous solution.