Introduction ochomy a he mame ges the Bdge berwer ely amd chemi ad, sn esecemcompase te ty of al ‘homial sipecs ofthe Each and thew mierpeanon wing the frp cba 1.1 Units of measurement ‘A unit of measurement isa definite magnitude ofa physical (quantity, defined and adopted by convention and/or by law, that is wed as a standard or measurement ofthe sme physical Quantity. Any other value of the physical quansry can be ‘expressed as a smple multiple ofthe unit of measurement. “The orginal metric eystem of measurement was adopted in France in 1791. Over the years st developed into two some- what different systems of metic unis: (a) the MKS system, based on the meter, kilogram, and second for length, mas and time, respectively; and (b) the CGS system (which was tmerodeced formally by the Brith Association for the Advancement of Science in 1874), based on the centimeter, tram, and second, There ate other tradicional diferences Beeween the two systems, for example, inthe measurements of clectic and magnetic fields. The recurting need for conversion from units in one of the two systems ro units of the other, however defeated the metric ideal of 2 universal measuring syetem, and a choice had to be made berween the two systems {or ioternatonal usage. in 1954, the Teoth General Conference on Weights and Measures adopted the mets kilogram, second, ampere, degree Kelvin, and candela as the basi units forall international ‘weights and measures. Soon afterwards, in 1960, the Eleventh General Conference adopted the name International System of Units (abbrevated to SI from the French “Systéme Parkas and shams (1950) Incernational Units”) for this collection of units. The * degree Kevin” was renamed the “kelvin” in 1967. LAA The Stsystem of units In the SI system, the modern form of the MKS system, there ace seven base units from which all other units of measure- ‘ment can be derived (Table 1.1). The lnernational Union of Pure and Applied Chemisty (TUPAC) has recommended the use of SI units in all scientific communications. This is ceranly destable from the perspective of standardization of ddata, but 2 lor ofthe available chemical data were collected riot r0 1960 and thus are not necssanily in SI units. It therefore necessary for geochemits to be familar with both SL and non-SI units, Equivalence between SI and non-SI units, and some of the commonly used physical constants are given, ‘Appendix 1 ‘Most chemists, physicists, and engineers now use SI system of units, but the use of CGS (centimerer-gram-second) and other non-SI units s still widespread in geologic literature tn this book we wil use ST units, bur wth two exceptions. As pointed out by Powell (1978) and Nordstrom and Munoz (1994), the ST unit pascal (Pa) unwieldy for reporting seological pressures. For example, many geochemical meas taements have been done at 1 atmosphere (atm) ambient pressure (the pressure exerted by the atmosphere at sea level, Which translates into 101,325 pascals or 1.01 megapascals nodacon 0 Gaochoatry Principles and Appbanos, Fist ton. Kl Ma {©2012 Kala © Mara. Pblabed 2072 by Rackwell Pubing is eee ee~T 2 Introduction “Tle 1.1 The base wi and examples of Serie woes ‘amples ofS derived units ae nt 2 Definition in terms. me Symbol ofthe Tas ts pat quonty Namely quay peronN oe, ong weer Force ' mo mika stim? oe Mogae fT a ee enn feowvure can? k fear oarge cusene S ee Tenor ance Wena etcpoenatiteence y ous teacaret ® Nome eS eas Tee tecety Gonos od Raccoon sem ewon-tne ce tat wil aclrate amas gby 18 Posaltbe peas ented fore of 16 ac Jean Peame enero eof 1 produce a elcome of mn Varn va arent 1 "ne recon ofthe fre (apa ater cumbersome number fo se. Mos gochett iene br ay che uni of pressare, which can ea be FEpveed no pac (1 har=10 pescals or 0.1 MPa) and Sihch is clove enough £9 premure expressed in atmaspbere Marco 987 atm! for the diference to be ignored ia most Cre Shou inoducing sigieant roe A sir problem ie rhe we of the Suni joule (instead ofthe more fillar nom t unt alo (a). Te calor, defined as che ‘easy af bat reed ro rase 1 gram () of water fom Peo ss, has a physical meaning that easy to under fend, Moreover tables of thermodynamic dats, especially fhe older omen we calories instead of joules. Ths, we may IRE Slonim the clculsons and repor the inal eu in joule (Leal=4.t84)) . ‘The faa sr scale of temperature is the Celsius scale (°C), neh Bcd on wo reference points for remperatur: the cepeite the emperarore at which ice i in equilibrium ‘Sotlngld water at atm pressure: nd the steam point, the CCiperstre at which steam i in equilibrium with liquid ‘Sidra Tam pressure, The Celis sale arbitraiy assigns Tlaperature of ero tothe ce point and a temperature of {ote the tam point The Sl uit of temperature kelvin (Ky, which he remperaurewsed in all thermodynamic {Giealaons If presure-temperaar (°C) plots at different ‘Slam are constructed for any gs the extrapolated lines IM esect at 2 point representing zero pressure at a temperatre around “273° (Fig. 1). This temperaan, Teh os or physically atunable (although it has been Tpyroached very closely, walled the absolute zero of temperature. rs the remperatue at which the molecules of Ws have 0 tanslavonal, rotational, or vibrational tnovion and cherefre no thera energy. The temperature Seale with abslae ner a the starting point i the kelvin tenpraare cle andthe ni of temperate om hs sale te kei (K, not *X), so named afer Lord Kelin who proposed icin 1848. The Kelvin ant of temperature is Akfined ws the 7273.16 faction ofthe so-called tiple point “ais 0100200 Temperate () Fig 1 The definition of absolute ero of emperatare. The lines VV show the variation of difleren volumes of asa a fancion of temperature and presare, When extrapolated the lines intersect a pote presenting sero pes at a temperature around -273°C. This Tempratre whch ne physiallarairale, sell the absolure zermof temperate for H,O (the temperature at which ice, liquid water, and steam coexist in equilibrium at atm pressure), which is (0.01K greater than the ice point. Thus, the ice point, which is defined as 0°C, corresponds to 273.15 K (see Fig. 4.3) and hip between kelvin and Celsius scales of Tik)=1(°4273.15 aayEales amon 10 crependo 95K follows frm equation 11) that the degree Cela oul magnitude othe Lei, which turn peta the aoe sl ae of «gen tempera ference o tempers interval isthe same whether ts expend inthe one eee Cebus C) orm he unit kn in the USA emperaaes are often measured nthe Fahenhesale(F Te expreae telating temperatures inthe Celsus and Fa sling temps ind Fahrenheit scales 1.12 Concentration u for solutions Conceations of slates sled subs) in solos (ella, or gsc) are comment expen cae mast concenrions pre ermine ligase hy or equivalent weight pet ie or mult Someerey (mary, molar or mol acto: Tbe oan the mabe fol abreast of se sancti amount of he subtance (pam etd tramolelr weight to oham he mae cone tae Seance the number of mols oth sobsence dd byte to number of males nthe oon ce econ 2 a ther elaboration. For example the mole acon of Nal (gammaleculrweyhtes8-t4)'n a salon of 100g of Nacl in 2g of H,0 (grammoleclrweghe8 0} em be Calaited a follows Number of moles of NaCl=100/58.44=1.7112 [Number of moles of H,0=2 (1000)/18.02111.1111 ‘oral number of moles in the solution= 1.7112 + 111.1111 = 112.8223 Mole fraction of NaCl in olusion=1.7112/112.8223=0.0152 Nore that the mole faction of a pure substance (sold, liquid, ‘or gas) is unity ‘The concentration units mg/L and ppm a8 well as molality and molarity are related through the density ofthe salution (pi: “Table 1.2 Concentration units for a sore Concentration uit Definition Miligrams per iter (malt) Mass of solute (a) volume of ‘solaion (0) ‘ars per milion (ppm) Masso solute (mg) mass of solution i) Mole faction 0 Mole of solute total moles of ‘olution’ pew Molarty (M1 Moles of solute volume of solution () Molly (im) Mole of solute mass of solvent kg) Normality Equivalent weight of solute (9)/ volume of solution (\) ‘ols ofa bstnce-weight ofthe tance (ram molec welght ofthe bance 1.2 The Geologie Time Se oncentation of vole gL conceraion ppm) = 2, the enry level ofthe 4s ona is lower than that of the three 3d orbitals, and the relationshy ewe and 4d ba ad eee ran 8d23 The ground state electron configuration of elements 17 ‘Table 2.3 The clearonic configuration ofthe element of the fire tre period, sell coat Maren) tation for electronic Bement 2 % 2 2, 2, 2, 3 39, 3p, 39, __ configuration # 7 w He " " w tt 1 teat te 1 1 13s 8 tl a 152529! fe 1 nt 5262p? " " nt t W229 ° " un i wasnt F 7 nou 1 e229 Ne i non nu 152829" Na 1 non faa teas 2038 Ms a on thirst wasp al rt non inte fi 182529539" si " ot Tid dhticet Was 2s" r n now Hoo Tt oT of aeaparae s i non honk th ott raeaeearape a uot Hoon ONT amaezpasaet a th 1h Th TL TLL teaeapaeape 2.3. The ground state electron configuration of elements ‘The ground state ofan isolated atom i ts quantum state of lowest permissible energy. The distribution of electrons among, various electron “shells” of an atom corresponding «0 the ‘quantum state of minimum energy is called the grovnd state ‘electron configuration. An atom is said to be in an excited state ft has a higher energy than the ground state because of ‘one or more ofits electrons occupying one or more “shells” of| higher energy compared to the ground state 2.21. Filling atomic orbitals with electrons: the Aufbau principle “The ingle eletron nan H atom (21) enters the orbital with the lowest energy (I Subject othe Pals exclasion prin pletheeletrome configuration of atoms of creasing toric umber is constructed by adding appropriate mamber of es= trons depending onthe atomic number) ro the posible ob tlsina way that minimizes the nergy ofthe atom, because the lowest energy state ofan atoms x most stale (or ground) state Ths fling-up proce scaled che Aufbau mcaning ul up")procipl, wich governed by the following st of gudelines (Companion, 1964; Evans, 196) (1), Because of unsystematic variations in energy levels of atomic orbitals as a function of quantum numbers and (Fig. 2.7) (i electrons are assigned to orbitals im order of increasing value of (n+/) and (i) for subshells with the same value of (+f, electrons are assigned fist 0 the subshell with lower n. For example, the Ss orbital (r+l=540=5) would fill before the 4d orbital (nsl=442 = 6), and the 4d orbital before the Sp orbital (n+1=5+ 1=6) because 4d has a lower value of The sequence in which orbitals are fille is: 15,25, 2p, 3s, 39,45, 3d,4p, 58,4, Sp, 68,4, 5d, 6p, 75 6d (2), No two electrons may have identical ses of the four {quantum numbers (Paul's exclusion principle). G) As many of the orbitals as possible are occupied by a single electron before any pairing of electons takes place (see Table 2.3; the unpaired electrons have parallel spins, and the paired electrons have opposite spins (Huds rule fof maximum mudtipliaty). This 18 because, even with Pairing of spins, two electrons chat aren the same orbital repel each other more strongly than two electrons in diferent orbitals ‘The rules listed above should be considered only as. a guide ‘opredictingelectron distribution in atoms. The experimentally determined electron configurations of lowest total energy do not always match those predicted by these guidelines, especially for the B group elements of the Periodic Table (see section 2.3.2), The electronic configurations of isolated atoms in the round state are presented in Appendix 2. Alternative elec tronic configurations may have to be considered for atoms in fected states or when they are not isolated (e.g. when involved in chemical reactions) aa» 18 Atomic Structure 23:2 The Periodic Table The Periodic Table reflects an attempt at a systematic ‘organization of the elements from the perspective of their atomic structures. In 1869, .wo very similar arrangements of the known elements, much like the modern Periodic Table (Fig, 2.8), were published independently one by the Russian chemist Dimitri Ivanovich Mendelees (1834-1907) and the ‘other bythe German chemist Lothar Meyer (1830-1895). Both were based on regular periodic repetition of properties with Increasing atomic weight of the elements, Mendeleev's largely ‘on chemical properties and Meyer's on physical propertcs. The ‘modern version ofthe Periodic Table organized on the basis ‘of atomic number ofthe elements, a concept that was developed some 50 years later than Mendeleev's work and is more fundamental to the identity ofeach element. ‘The vertical columns inthe Periodic Table are referred to a8 sroups, and the horizontal rows are referred to as periods, which are numbered in accordance with the first quantum number of the orbitals that are being filled with increasing atomic number, For example, electrons fill the Is orbital n clements belonging to the Ist period, 2s and 2p orbitals in clements of the 2nd period, and 3¢ and 3p orbitals in elements ofthe 3rd peri. The electron disenbution in elements included tn the 4th to 7th periods becomes more complicated because of fillmg of d and f orbitals (3d, 4d, Sd 6 47, 5) as illustrated in Fig. 2.8. ements within a period have properties that change progressively. with increasing atomic number because of addition of electrons. In contrast, elements in any group have smilar physical and chemical properties because of similar Mee) On the bass ofthese two parameters, the elements may be divided into three broad categories: electron donors (metals); electcon acceptors (nonmetal), and noble element (inert gas) 2.6 Recapitulation Terms and concepts Anions Auibau principle ‘Avogadro's number Azimuthal quantum number Bohr radius Cations Electron affinity lectron accepcors (nonmetal) lectron donors (metals) Excited state ed| | | | | 22 Atomic Structure ae tg Ground state Hund’s rule Tonization potential Inert elements Isobars Isorones Isoropes ‘Magnetic quantum number ‘Meralloids (semimetals) ‘Molar mass Mole Nodal plane Octet tale Pauli’s exclusion principle Periodic Table Principal quantum number Schrodinger equation Screening effect Spin quantum number Standard temperature and pressure (STP) ‘Transition elements Valence electrons ‘Computation techniques * The atomic weight (in amu) ofan element from the data on the abundances of its isocopes. * Ionization potential, electron affinity 2.7 Questions 1. Show that !amu=1.6606x10"g [Hints Jamu= 1/12 of the mass of :C contains 6.022% 10" atoms.) Calculate the atomic weights |in amu) ofthe elements U and Pb from the abundances of their isotopes given below: 52C atom: I mole of 10. 5. Ageologist has i ca hg wis i L305 ole of liter of the solution at 25°C tempera- mal of AaCl Pt cena the mae of diced [AgCl in 1L of the solution. Gram atomic weight ofthe dlements: Ag=107.87; C1=35.453. Calculate the number of H,O molecules that will evapo- Gee i ha one op Of water he fs pe cons gatokramier=e 22004 ee ton depts One of hen eon of nape P04, a oe St mt of nets Po and Se eet 09 bse on en 30 lies of 0 ae poate com se Gram tome weigh of ee carr 85,0% 1600 ‘What is the maximum number of electrons that can be Met patna semi ora eae goats ale rials tn edt xb wi nS eee pee mas deo cotgarica of wong cen ne as (Ze37h Xeon (2=S4) and Cran 9) dae ce mato Table 23, prepare ble dees ered Alig wih cos of he mea a etd enter res Tee I ofan reno xin of te tteonagetc dation secrun ata Seeny of specrumbasa eons of 520 0%5" Uy cal ewarceghcomeponding ich of ere Uy Chala how muchnore the ene acted ths plows ef nese! Rg enSfael crt mabe Be Waa'be wm asoited wi «neuro o me LoreclOsgaeing cab peter tacos [A saturated sol = ae sore srs SS es ment ar 3 Ee is = ge 3 Se 22 RB mB 2B3 Chemical Bonding The ores sponse for chemical comnaton of toms are of neo main type. There are those ores bch arse between elec cally charged specs, repulse the charges ae soma, atacve Wf dismdat The second pe of force may be elled on ‘xchange force nd hac cm be described mtr of he bringer eae eatin. A ile reflection wl revel tha te wader ‘and nether alae hove sto ways of deer different imation, nd all probably the ong of oth forces the sae. Chemical compounds are formed by the combination of two of more atoms (or ions), and the formation of a stable compound occurs when the combination results in a lower energy than the total energy of the separated atoms (or fons). Interatomic (or inteionic) net attractive forces that hold atoms (or 1ons) in solids together are called chemical bonds. Chemical bonds usually involve only the valence electrons (s and p electrons in the ourermost orbitals) of an atom. Physical and chemical properties ofall substances depend fon the character of the chemical bonds that hold them together. ‘Much of the bonding in solids of geochemical intrest can be described in terms of wo end-member types: (i) tonic (or clectrovalent) bonds that exist because of electrostatic attrac: thon between cations and anions formed by transfer of one oF more electrons between atoms; and (u) covulent bonds that are because of sharing of electrons between atoms that fesults from overlap of orbitals from the two atoms. For ‘sample, the ionic bonding in NaCl resus from the electro ‘atic artraction berween a Na” cation formed by the loss of alence electron from the 3s orbital of the Na atom (1e2e2p"3s!) and a Ch anion formed by incorporation of thatelectronintothe 3porbital of the Clatom (1=°2s°2p*353p") (Fig 31a): nero to Geochertry: Primi Sona nals Chora Publ 2012 by Blackwell Publishing Ld Fyfe (1964) Na (122229634!) = Nar (15226294) + CL (12822p 3283p!) +e = Cr (152822p363p) 2Nay, + Clyy = 2Na'Ch;, The NaCI molecule itself is electrically neutral because its structure contains a Na” cation for every Cl anion. Sodium and chlorine atoms combine readily because of the large dit ference in thei fist ionization potential and electron affinity (see section 24), Covalent bonding, on the other hand, arises from sharing of electrons. The covalent bonding in Cl, for example, may be viewed as resulting from the sharing of a pair of eleerons between two Cl atoms, eich of which contributes ‘one electron to the shared pair (Fig. 3.1b). Atoms can share ‘one, two, or thre electron pais, forming, respectively single, ‘double, and tiple covalent bonds. All bonds between atoms of| diferent elements have some degree of both ionic and cova: dent character. ‘Compounds containing predominantly ionic bonding are called ionic compounds, and those that are held together inainly by covalent bonds are called covalent compounds. ‘This diference in bonding accounts for the differences in some properties associated with simple ionic and covalent Compounds (Table 3.1) Other types of bonds that wall be diss cussed briefly inthis chapter include metalic bonds, Van der Waals bonds, and hydrogen bonds es and Applications, Ft Fdtion Kala C. Mas24 Chemical Bonding (@) nie bonding in Nac Fg 3.1 Lew dor representation ndings NCD ad) ‘ale bnding (Ce ne Kind of dasration, the chem bol ofthe emer inthe ner complee sel of caro, al the alone dectons (.,lecrns tte otermont cried and p ob) are repseed by dots The rl oalet bond I ees by the ‘wo dts of the “honding pure by sage eres ht pi ay put of pshared dcrone the sae oral whch doesnot paren the formation of covalent nds are elem a le pa” 3.1. Ionic bonding 3.1 Tonic radié ‘The potential energy of a system (E,) comprised of wo oppo- sitely charged ions (eg, Na* and Cl), each with it electron loud around he nucleus, approaching each other s given by rf, 1964): 3 Gn) “Table 3.1 Some proprio onc and covalent compounds hac hi tcl tee, inne: bre ee er apiinimadomiane Seer S aegced whee aoe beet eee a. ete ee between the opposite net charges (eh and the term ce bere ne aan mere g Fp aie partly Gena he ek ees ita cea tion, s assigned a negative sign) becomes more negative, nds, foc rape cone pipet epee a ee pe om engl pas pally a renetien reel eat ae eae ae Sere tale ucamian iacoe et se a haces te oer sal ie se Se eater adden A bea ee eee gained ries Peer eaecinl teeter ee ee cman aicersieimar oe Som ie assenmaree ss Siete asecmin csi Facet Eig id bopialafall someenoc! eee askas dds cose ee eae ti esis beats aac Count ae See eee Seren A casipeoaee eee ae ral 92s boned aes ahah eee Beretta accu natin aero ie ae es cea eee eh aed alana eae eer one Seach tebe eee eee Sea en ee pala eairepatahel peters Covalent compounds Property tonic compounds Panicipating Commonly beeen two elements with quite ‘lerents citferent electronegatvtis, usualy a metal {anda onmeta! Melting point They are slits with high melting points (typically > 400°C) lone compounds donot exist as gases solaiity ae soluble in polar solvents sch a wate, ‘and mos are insoluble n nonpolar solvents such a carbon tetrachloride (EC), Becta ‘Molten compounds and aqueous solutions are ‘conductivity good conductas of electra because they ‘Contain charged parties ons) see eion 365, Commonly between two elements with similar ‘electronegative’ usually nonmetal. Homonuclear molecules (suchas Gl, comprised of only one element) are covalent They are gases, liquids, o¢ sls with low malting points, (pally «300° "Many ae insluble in polar solvents, and mos are soluble in ‘onpolar solvents such as carbon tetrachlonise (Ll),; Mien aR -Atracton ON Intron distance (A) —= Fig 32 Variation ofthe potent energy (Fosse contig of sg carged oton anda singly charged anon a uncon of teem darance The equlibam ern tance (marked by ‘he minemam vale of Ey when 4EUR=0 Foe R>R. Ese ‘ermine by the cube atracon bree the oppo charge ah for ReR, bythe repulsion bewece the nck and the sae cod, For the discussion below, we assume a model of pure ionic bonding arsing out of a geometric framework of ions repre= sented by hard spheres of constant radi. But how do we determine the eadius of each son? Actually itis not posible ¢o measure the radius of individual ios ina solid, but we ean ‘measure the interionic distance between centers of two ions in ‘sold from is cll dimensions determined with X-ray diffrac- tion techniques, and then determine the radius of individual tons through sonie manipulation (Companion, 1964). For the ‘Purpose of illustration, let us suppose that Fig. 3.3 represeas the packing in LiCl and KCI crystals as revealed by X-ray dlifraction data It is reasonable ro expect that Li’, with only ‘peo electrons, very small cation and assume thatthe pack: ing im LiCl be largely determined by the much larger Clan ‘ons (each containing electrons) touching each other. In this ‘ease the radius ofthe Cl ion ("-) is onehalf ofthe measur Sable interiomic distanced, We can now determine the radius ‘of K: ton from the measured inteioni distance d, ina KCI crab 1, = dy—r,_ Ieturns out thar the ionic radi cake lated by this strategy are reasonably constant from compound uc co te 82 lente Fig. 33 Seratey for demining onc radi from packing of 08 {assumed ob hard spheres LiCl and KCL 3.1 lomic bonding 25 has enabled the setting up a self-consistent set of average sonic radi (Fig. 3.4). ‘As expected, ionic radii of cations and anions vary with atomic number The radius ofa given won is also a function of ‘the coordiation munber, the number of nearest neighbors of the on na crystalline strucure sce ection 3.1.2}-Some general trends for ionic radit (expressed an A) with octahedral (or six- fold) coordination (Fg. 34), the most common kind of coord natin for most ions in slicate minerals are summarized below: (1), Cations ate smaller than anions, the only exceptions boeing the five largest cations (Rb*, Cs", Fr, Ba, and Ra), which are larger than F> she smallest anion. (2) Within an ssoclectromie series series of ions with the same number of electrons ~ sonic radius decreases with Increasing atomic number because of increased nuclear artacoon forthe elctton cloud. For example, rl O48) < (0.54) <1 (0.72) <7, (102) <7 (138) 1.0 for CN = 12 {edge-centered cubic coordination) (Fig, 3.6) Other coordina tion numbers, such as, 7,9, 10, and 11, do exist bu are quite lincommon because such coordination polyhedra cannot be > = ee | ye, ee eo | mem EE ee | =e, na ; ae Lt : tno van She ae ee Se ot a = of = ei | Fig 3.6 The er ofr ads rtn on cordnatin uber and posse ometralarargemen of os nme etal ZS } (opal sel no tom: compound bar same en the | sac: becuse is th max commen compnd in which he ‘rometnal aetangenent oscars (van, 1968). { extended into infinite, regular shree-dimensional arrays (Greenwood, 1970). In mineral structures, the most common anion is O°, which has an ionic radius of 40 A, and the tonic radi of most common cations ate hetween 0.60 and 1.10 A. ( Thus, the radius ratios with oxygen in minerals mostly he Derween 0.43 and 0.79, suggesting that the most frequent coordination number in finerals is 6. his is why Fig. 34 ists | tonic radi for octahedral coordination rather than for ttrahe- dral or cubic coordination. Examples of some ionic crystal struetutes characterized by different coordinations are presented in Fig. 37 ‘Many cations in silcate minerals occur exclusively in a parscular coordination with oxygen, but some occur in more than one coordination, to some extent controled by the temperatute and pressure of erystallzation, For example, the radius ratio of AD” bonded to O is 0.54 ALO A = 0.386, which is very close to the theoretical boundary of 0.414 between CN=4 and CN'=6,Thus,in silicate minerals formed