Oakland Schools Resource Unit

Chemistry

Intermolecular Forces
Brook R. Kirouac David A. Consiglio, Jr. SouthfieldLathrup igh School Southfield !u"lic Schools

Bonding: Intermolecular Forces

Content Statements: C2.2: Chemical Potential Energy Potential energy is stored whenever work must be done to change the distance between two objects. The attraction between the two objects may be gravitational, electrostatic, magnetic, or strong force. Chemical otential energy is the result of electrostatic attractions between atoms. C!.!: "eating #m acts "eating increases the kinetic $translational, rotational, and vibrational% energy of the atoms com osing elements and the molecules or ions com osing com ounds. &s the kinetic $translational% energy of the atoms, molecules, or ions increases, the tem erature of the matter increases. "eating a sam le of a crystalline solid increases the kinetic $vibrational% energy of the atoms, molecules, or ions. 'hen the kinetic $vibrational% energy becomes great enough, the crystalline structure breaks down, and the solid melts. C(.!: Pro erties of )ubstances *ifferences in the hysical and chemical ro erties of substances are e+ lained by the arrangement of the atoms, ions, or molecules of the substances and by the strength of the forces of attraction between the atoms, ions, or molecules. C(.(: ,olecular Polarity The forces between molecules de end on the net olarity of the molecule as determined by sha e of the molecule and the olarity of the bonds. C-.(: Phase.Change *iagrams Changes of state re/uire a transfer of energy. 'ater has unusually high0 energy changes associated with its changes of state.

Content Expectations: C2.1c: Compare qualitatively the energy changes associated with melting various types of solids in terms of the types of forces between the particles in the solid. C3.3B: Describe melting on a molecular level. C .3!: "ecogni#e that substances that are solid at room temperature have stronger attractive forces than liquids at room temperature$ which have stronger attractive forces than gases at room temperature. C .3c: Compare the relative strengths of forces between molecules based on the melting point and boiling point of the substances. C .3d: Compare the strength of the forces of attraction between molecules of different elements. %&or e'ample$ at room temperature$ chlorine is a gas and iodine is a solid.( C .3f: )dentify the elements necessary for hydrogen bonding %*$ +$ and &(. C .3g: ,iven the structural formula of a compound$ indicate all the intermolecular forces present %dispersion$ dipolar$ hydrogen bonding(. C . a: -'plain why at room temperature different compounds can e'ist in different phases.
C.. c: -'plain why both the melting point and boiling points for water are significantly higher than other small molecules of comparable mass %e.g.$ ammonia and methane(

Instructional Background Information: Melting on a Molecular Level: /elting involves the disruption of the crystal lattice of a solid via the absorption of 0inetic energy by the molecules in the lattice from their surroundings. !s the forces holding the lattice together increase in strength so does the melting point of the solid. Strong Forces: )onic bonding$ metallic bonding$ and networ01covalent bonding. 2trong intermolecular forces result in room temperature solids with high melting and boiling points. Metallic and Network Bonding is difficult to quantify. Ionic Bonding: )onic bonds are the result of electrostatic attraction between positive and negative ions. )onic bonding is directly proportional to ionic charge and inversely proportional to ionic si#e. eak Forces: 3ydrogen bonding$ dipole1dipole interactions$ 4ondon dispersion forces. !"drogen Bonding: 3ydrogen bonding is the unusually strong dipole1dipole interaction that occurs when a highly electronegative atom %*$ +$ or &( is bonded to a hydrogen atom. 5his bond nearly strips the hydrogen atom of its electrons leaving$ essentially$ a na0ed proton. 5his proton is highly attracted to the electron pairs on nearby molecules. 3ydrogen bonding is significantly stronger than the dipole1dipole interactions which are in turn stronger than 4ondon dispersion forces. 3ydrogen bonding e'ists only in molecules with an *13$ +13$ or &13 bond. #ipole$#ipole: Dipole1dipole interaction is the attraction between a partially negative portion of one molecule and a partially positive portion of a nearby molecule. Dipole1dipole interaction occurs in any polar molecule as determined by molecular geometry.

www.lbl.gov6images6/icro7orlds632+31bond.gif

Dipole1Dipole )nteraction

3ydrogen Bonding %unusually strong Dipole1Dipole(

London #ispersion: 4ondon dispersion forces result from instantaneous non1 permanent dipoles created by random electron motion. 4ondon dispersion forces are present in all molecules and are directly proportional to molecular si#e. Effects of Intermolecular Forces: 5he strength of intermolecular forces present in a substance is related to the boiling point and melting point of the substance. 2tronger intermolecular forces cause higher melting and boiling points. -8!/94-2: C3 1 /ethane: has only very wea0 4ondon dispersion forces %lowest b.p. : m.p.( C3Cl3 1 Chloroform: has dipole1dipole interaction %moderate b.p. : m.p.( *33 1 !mmonia: has hydrogen bonding and dipole1dipole interaction %high b.p. : m.p.(

%&e Forces 'etween Molecules !ll matter is held together by force. 5he force between atoms within a molecule is a chemical or intramolecular force. 5he force between molecules is a physical or intermolecular force. 7e learned about intramolecular forces and the energy it too0 to overcome these forces$ earlier in our chemical studies. *ow we will focus on intermolecular forces. %&e Nature of Intermolecular Forces:

5he )ntermolecular &orces %forces between molecules( are wea0er than )ntramolecular &orces %5he Chemical Bonds within an )ndividual /olecule(. 5his distinction is the reason we define the molecule in the first place. 5he properties of matter result from the properties of the individual molecule %resulting from chemical bonding( and how the molecules act collectively %resulting from intermolecular forces(.
)ntermolecular &orces are longest1ranged %act strongly over a large distance( when they are electrostatic. )nteraction of Charge /onopoles %simple charges( is the longest1

ranged electrostatic force. C&arge$C&arge forces %found in ionic crystals(

&or li0e charges %;$;( or %1$1($ this force is always repulsive. &or unli0e charges %;$1($ this force is always attractive. C&arge$#ipole &orces: !n uncharged molecule can still have an electric dipole moment. Electric #ipoles arise from opposite but equal charges separated by a distance. /olecules that possess a dipole moment are called (olar molecules %remember the polar covalent bond<(. 7ater is polar and has a dipole moment of 1.=. Debye. 5he Debye is a unit of dipole moment 13? and has a value of 3.33> ' 1? Coulomb meter. 7hen salt is dissolved in water$ the ions of the salt dissociate from each other and associate with the dipole of the water molecules. 5his results in a solution called an Electrol"te

5he force may be understood by decomposing each of the dipole into two equal but opposite charges and adding up the resulting charge1charge forces. *otice that the Charge1Dipole &orces depend on relative molecular orientation. 5his means that the forces can be attractive or re ulsive depending on whether li0e or unli0e charges are closer together. +n average$ dipoles in a liquid orient themselves to form attractive

interactions with their neighbors$ but thermal motion ma0es some instantaneous configurations e'ist fleetingly that are$ in fact$ repulsive. #ipole$#ipole forces e'ist between neutral polar molecules. !gain$ this force may be understood by decomposing each of the dipole into two equal but opposite charges and adding up the resulting charge1charge forces.

5he following table demonstrates the effect of the dipole moment on the boiling point of several substances: *ormal Boiling 9oint @BA 231 2 = 2 C 2C 3..

2ubstance 9ropane Dimethyl ether Chloromethane !cetaldehyde !cetonitrile

/olecular /ass @g6molA

Dipole moment @DebyeA ?.1

> .?

1.3 2.? 2.D

3.C

-lectrostatic forces are defined %categori#ed( by the symmetry of the partners involved in the interaction. 5his symmetry is labeled by the first non1#ero moment of the charge distribution$ i.e. /onopole$ Dipole$ Euadrupole$ etc. -lectrostatic forces only e'ist between molecules with ermanent moments of their charge distributionF /olecules do not have to distort or fluctuate in order to e'hibit electrostatic intermolecular forces. -lectrostatics cannot e'plain the whole story$ however. /olecules that are round and have no charge have no electrostatic forces between each other. 3ow$ then$ do round molecules form liquids or solids< Inductive Forces and #ispersion Inductive forces arise from the distortion of the charge cloud induced by the presence of another molecule nearby. 5he distortion arises from the electric field produced by the charge distribution of the nearby molecule. 5hese forces are alwa"s attractive but are in general shorter ranged than electrostatic forces. )f a charged molecule %ion( induces a dipole moment in a nearby neutral molecule$ the two molecules will stic0 together$ even though the neutral molecule was initially round and uncharged:

+ther inductive forces e'ist %permanent dipole 1 induced dipole$ etc.( but this one %charge1induced dipole( is the strongest. )nductive forces that result not from permanent charge distributions but from fluctuations of charge$ are not called inductive forces at all but are called London #ispersion forces. 5hese forces are ubiquitous but are most important in systems that have no other types of molecular stic0iness$ li0e the rare gases. 5he rare gases may be liquefied$ and it is dispersion forces that hold the atoms together %no electrostatic or inductive forces e'its(

5he movement of the electrons$ even in the 3e atom$ causes an instantaneous dipole to be formed. 5he time1averaged dipole moment of the atom is still #ero. 5his dipole$ however fleeting$ can induce a dipole in a neighboring atom$ causing a force. 5his force is always attractive but even shorter ranged %and wea0er( than permanent dipole1 induced dipole forces. Si)e %Golume and 2hape( determines the magnitude of the dispersion force. The bigger the si1e, the larger the dis ersion force.

!"drogen Bonding

5he figure above shows the normal boiling point temperatures for several related substances. 5his boiling point diagram tells us about the intermolecular forces between a homologous series of small hydrogen containing molecules. 4oo0 first at the ,roup I* hydrides$ from C3 through

2n3 . 5he boiling points of these molecules increase with increasing mass$ as one would e'pect. 5he group *I hydrides do the same thing$ with

the notable e'ception of 7!5-"H ! special type of intermolecular force e'ists between water molecules called hydrogen bonding$ which raises its boiling point significantly with respect to its isovalent homologs. 3ydrogen is unique among the elements because it has a single electron which is also a valence electron. 7hen this electron is hogged by another atom in a polar covalent bond$ a significant fraction of the hydrogen nucleus becomes uncovered and the bare nucleus desperately see0s to be covered by electrons from other atoms %modesty<(. ! 3ydrogen Bond is the attractive interaction between two closed shell species that ... arises from the lin0 of the form !13 B$ where + and B are highly electronegative elements and B possesses a lone pair of electrons. *ormally$ hydrogen bonds only e'ist when atoms + and B are *itrogen$ +'ygen$ and &luorine. )f the element B is 1 anionic %such as Cl ( and thus a very good electron donor$ it may also participate in hydrogen bonding. 3ydrogen bonding is very important the function of proteins$ as these interactions determine the way they fold %their shape($ and this determines how they react in the cell. &luorine hydrogen bonds not found too often in biochemistry$ but can be important in certain synthetic materials properties. Summar" of %"pes of Intermolecular Forces

http:66www.chem.ufl.edu6Iitl62? .6lectures6lecJg.html

%&ree t"pes of force can operate 'etween covalent molecules: Dispersion &orces also 0nown as 4ondon &orces %named after &rit# 4ondon who first described these forces theoretically 1C3?( or as 7ea0 )ntermolecular &orces or as van der 7aalKs &orces %named after the person who contributed to our understanding of non1ideal gas behavior(. Dipole1dipole interactions 3ydrogen bonds

"elative strength of )ntermolecular &orces: )ntermolecular forces %dispersion forces$ dipole1dipole interactions and hydrogen bonds( are much wea0er than intramolecular forces %covalent bonds$ ionic bonds or metallic bonds( dispersion forces are the wea0est intermolecular force %one hundredth1one thousandth the strength of a covalent bond(F hydrogen bonds are the strongest intermolecular force %about one1tenth the strength of a covalent bond(. dispersion forces L dipole1dipole interactions L hydrogen bonds

Dispersion Forces (London Forces, Weak Intermolecular Forces, van der Waal's Forces) are very wea0 forces of attraction between molecules resulting from: momentary dipoles occurring due to uneven electron distributions in neighboring molecules as they approach one another the wea0 residual attraction of the nuclei in one molecule for the electrons in a neighboring molecule. 5he more electrons that are present in the molecule$ the stronger the dispersion forces will be. Dispersion forces are the only type of intermolecular force operating between non1polar molecules$ for e'ample$ dispersion forces operate between hydrogen %3 2( molecules$ chlorine %Cl2( molecules$ carbon dio'ide %C+2( molecules$ dinitrogen tetro'ide %*2+ ( molecules and methane %C3 ( molecules. Dipole-Dipole Interactions are stronger intermolecular forces than Dispersion forces occur between molecules that have permanent net dipoles % polar molecules($ for e'ample$ dipole1dipole interactions occur between 2Cl 2 molecules$ 9Cl3 molecules and C33Cl molecules. )f the permanent net dipole within the polar molecules results from a covalent bond between a hydrogen atom and either fluorine$ o'ygen or nitrogen$ the resulting intermolecular force is referred to as a hydrogen bond %see below(.

5he partial positive charge on one molecule is electrostatically attracted to the partial negative charge on a neighboring molecule. Hydrogen bonds occur between molecules that have a permanent net dipole resulting from hydrogen being covalently bonded to either fluorine$ o'ygen or nitrogen. &or e'ample$ hydrogen bonds operate between water %3 2+( molecules$ ammonia %*33( molecules$ hydrogen fluoride %3&( molecules$ hydrogen pero'ide %3 2+2( molecules$ al0anols %alcohols( such as methanol %C3 3+3( molecules$ and between al0anoic %cabo'ylic( acids such as ethanoic %acetic( acid %C3 3C++3( and between organic amines such as methanamine %methyl amine$ C3 3*32(. are a stronger intermolecular force than either Dispersion forces or dipole1dipole interactions since the hydrogen nucleus is e'tremely small and positively charged and fluorine$ o'ygen and nitrogen being very electronegative so that the electron on the hydrogen atom is strongly attracted to the fluorine$ o'ygen or nitrogen atom$ leaving a highly locali#ed positive charge on the hydrogen atom and highly negative locali#ed charge on the fluorine$ o'ygen or nitrogen atom. 5his means the electrostatic attraction between these molecules will be greater than for the polar molecules that do not have hydrogen covalently bonded to either fluorine$ o'ygen or nitrogen.

!!ect o! Intermolecular !orces on melting and boiling points o! molecular covalent substances" 2ince melting or boiling result from a progressive wea0ening of the attractive forces between the covalent molecules$ the stronger the intermolecular force is$ the more energy is required to melt the solid or boil the liquid. )f only dispersion forces are present$ then the more electrons the molecule has %and consequently the more mass it has( the stronger the dispersion forces will be$ so the higher the melting and boiling points will be. Consider the hydrides of ,roup )G$ all of which are non1polar molecules$ so only dispersion forces act between the molecules. C3 %molecular mass I 1>($ 2i3 %molecular mass I 32($ ,e3 %molecular mass I DD( and 2n3 %molecular mass I 123( can all be considered non1polar covalent molecules. !s the mass of the molecules increases$ so does the strength of the dispersion force acting between the molecules$ so more energy is required to wea0en

Boiling 9oints of ,roup )G

3ydrides

the attraction between the molecules resulting in higher boiling point.

)f a covalent molecule has a permanent net dipole then the force of attraction between these molecules will be stronger than if only dispersion forces were present between the molecules. !s a consequence$ this substance will have a higher melting or boiling point than similar molecules that are non1polar in nature. Consider the boiling points of the hydrides of ,roup G)) elements. !ll of the molecules 3& %molecular mass I 2?($ 3Cl %molecular mass I 3D($ 3Br %molecular mass I =1( and 3) %molecular mass I 12=( are polar$ the hydrogen atom having a partial positive charge %3 ( and the halogen atom having a partial negative charge %& $ Cl $ Br $ ) (. !s a consequence$ the stronger dipole1 interactions acting between the hydride molecules of ,roup G)) elements results in higher boiling points than for the hydrides of ,roup )G elements as seen above. 7ith the e'ception of 3&$ as the molecular mass increases$ the boiling points of the hydrides increase. 3& is an e'ception because of the stronger force of attraction between 3& molecules resulting from hydrogen bonds acting between the 3& molecules. 7ea0er dipole1dipole interactions act between the molecules of 3Cl$ 3Br and 3). 2o 3& has a higher boiling point than the other molecules in this series. !!ect o! Intermolecular Forces on #olubility )n general li0e dissolves li0e:

Boiling 9oints of ,roup G))

hydrides non1polar solutes dissolve in non1polar solvents 9araffin wa' %C3?3>2( is a non1polar solute that will dissolve in non1polar solvents li0e oil$ he'ane %C>31 ( or carbon tetrachloride %CCl (.

9araffin wa' will *+5 dissolve in polar solvents such as water %3 2+( or ethanol %ethyl alcohol$ C23.+3(. polar solutes such as glucose %C>312+>( will dissolve in polar solvents such as water %32+( or ethanol %ethyl alcohol$ C23.+3( as the partially positively charged atom of the solute molecule is attracted to the partially negatively charged atom of the solvent molecule$ and the partially negatively charged atom of the solute molecule is attracted to the partially positively charged atom of the solvent molecule. ,lucose will *+5 dissolve in non1polar solvents such as oil$ he'ane %C >31 ( or carbon tetrachloride %CCl (. )onic solutes such as sodium chloride %*aCl( will generally dissolve in polar solvents but not in non1polar solvents$ since the positive ion is attracted the partially negatively charged atom in the polar solvent molecule$ and the negative ion of the solute is attracted to the partially positively charged atom on the solvent molecule. http:66www.ausetute.com.au6intermof.html

IN%E,M-LEC.L+, F-,CES Introduction: 5he physical properties of melting point$ boiling point$ vapor pressure$ evaporation$ viscosity$ surface tension$ and solubility are related to the strength of attractive forces between molecules. 5hese attractive forces are called Intermolecular Forces. 5he amount of Mstic0 togethernessM is important in the interpretation of the various properties listed above.

5here are four types of intermolecular forces. /ost of the intermolecular forces are identical to bonding between atoms in a single molecule. )ntermolecular forces Nust e'tend the thin0ing to forces 'etween molecules and follows the patterns already set by the bonding within molecules.

/0 I-NIC F-,CES: 5he forces holding ions together in ionic

solids are electrostatic forces. +pposite charges attract each other. 5hese are the strongest intermolecular forces. )onic forces hold many ions in a crystal lattice structure. "eview 1 )onic Bonds

10 #I(-LE F-,CES: 9olar covalent molecules are sometimes described as MdipolesM$ meaning that the molecule has two MpolesM. +ne end %pole( of the molecule has a partial positive charge while the other end has a partial negative charge. 5he molecules will orientate themselves so that the opposite charges attract principle operates effectively. )n the e'ample on the left$ hydrochloric acid is a polar molecule with the partial positive charge on the hydrogen and the partial negative charge on the chlorine. ! networ0 of partial ; and 1 charges attract molecules to each other. "eview 1 9olar Bonds

20 !3#,-4EN B-N#IN4: 4in0 to more e'tensive discussion: !"drogen Bonding

5he hydrogen bond is really a special case of dipole forces. ! hydrogen bond is the attractive force between the hydrogen attached to an electronegative atom of one molecule and an electronegative atom of a different molecule. Osually the electronegative atom is o'ygen$ nitrogen$ or fluorine. )n other words 1 %&e &"drogen on one molecule attac&ed to - or N t&at is attracted to an - or N of a different molecule0 )n the graphic on the left$ the hydrogen is partially positive and attracted to the partially negative charge on the o'ygen or nitrogen. Because o'ygen has two lone pairs$ two different hydrogen bonds can be made to each o'ygen. 5his is a very specific bond as indicated. 2ome combinations which are not hydrogen bonds include: hydrogen to another hydrogen or hydrogen to a carbon.

50 IN#.CE# #I(-LE F-,CES: &orces between essentially non1polar molecules are the wea0est of all intermolecular forces. M5emporary dipolesM are formed by the shifting of electron clouds within molecules. 5hese temporary dipoles attract or repel the electron clouds of nearby non1polar molecules. 5he temporary dipoles may e'ist for only a fraction of a second but a force of attraction also e'ists for that fraction of time. 5he strength of induced dipole forces depends on how easily electron clouds can be distorted. 4arge atoms or molecules with many electrons far removed from the nucleus are more easily distorted. "eview 1 *on19olar Bonds

http:66www.elmhurst.edu6Ichm6vchemboo061>?!intermolec.html Classif"ing Intermolecular Forces

)n general$ intermolecular forces can be divided into several categories. 5he four prominent types are: 1. Strong ionic attraction "ecall lattice energy and its relations to properties of solid. 5he more ionic$ the higher the lattice energy. -'amine the following list and see if you can e'plain the observed values by way of ionic attraction: 4i&$ 1?3>F 4i)$ D3DF B&$ =21F /g&2$ 2C.D 0P6mol. 2. Intermediate dipole$dipole forces 2ubstances whose molecules have dipole moment have higher melting point or boiling point than those of similar molecular mass$ but their molecules have no dipole moment. 3. eak London dispersion forces or van der aal6s force 5hese forces always operate in any substance. 5he force arisen from induced dipole and the interaction is wea0er than the dipole1dipole interaction. )n general$ the heavier the molecule$ the stronger the van der 7aalKs force of interaction. &or e'ample$ the boiling points of inert gases increase as their atomic masses increases due to stronger 4andon dispersion interactions.

!"drogen 'ond Certain substances such as 32+$ 3&$ *33 form hydrogen bonds$ and the formation of which affects properties %mp$ bp$ solubility( of substance. +ther compounds containing +3 and *32 groups also form hydrogen bonds. /olecules of many organic compounds such as alcohols$ acids$ amines$ and amino acids contain these groups$ and thus hydrogen bonding plays an important role in biological science. 4. Covalent 'onding Covalent is really intramolecular force rather than intermolecular force. )t is mentioned here$ because some solids are formed due to covalent bonding. &or e'ample$ in diamond$ silicon$ quart# etc.$ the all atoms in the entire crystal are lin0ed together by covalent bonding. 5hese solids are hard$ brittle$ and have high melting points. Covalent bonding holds atoms tighter than ionic attraction. 5. Metallic 'onding &orces between atoms in metallic solids belong to another category. Galence electrons in metals are rampant. 5hey are not restricted to certain atoms or bonds. "ather they run freely in the entire solid$ providing good conductivity for heat and electric energy. 5hese behaviors of electrons give special properties such as ductility and mechanical strength to metals. 5he division into types is for convenience in their discussion. +f course all types can be present simultaneously for many substances. Osually$ intermolecular forces are discussed together with 5he 2tates of /atter$ which is lin0ed to a well illustrated web1 site. )ntermolecular forces also play important roles in solutions$ a discussion of which is given in 3ydration$ solvation in water. ! summary of the interactions is illustrated in the following diagram: