LECTURE 3(3 hours): CHEMICAL PROPERTIES OF MINERALS INTRODUCTION The chemical composition of a mineral is of fundamental importance.

Many of mineral properties depend on its chemistry and its crystalline structure. Atom: smallest subdivision of an element From 1H to 103Lr (FI! 3 ") Atom#$ Num%er: number of &. Atom#$ M'ss: (& ( n) Atom#$ )e#*ht: (& ( n) of an element which is a whole number and its elemental abundance compared to that of O+", Isoto&e: ame atomic number but different atomic mass and therefore different n. !".# %3' %3( $%& # $%& Ion:char"ed atoms. )l* 'n#on- +a, $'t#on .'len$e: number of electron lost or "ained. -%* Fe3, (FI! 3 /) Mole$ule: combined atoms with different bonds. Mole$ul'r )e#*ht: total atomic wei"hts of its components. R'0#$'l: stron" bondin" between two or more atoms. .+H/0,# .-H0*# . i-/0/*# .)-30%*. A$#0: compound of H, with an anion li1e )l* .H)L0 or a ne"ative radical .)030%* .H%)-30 1'se: compound of cation li1e +a, with a ne"ative radical .-H0* .+a-H0 S'lt: formed by a reaction of an acid and a base. H)2 , +a-H +a)l,H%)'ter o2 Cr3st'll#4't#on: some minerals contain free H%- molecule or .-H0* radical or both within its crystal structure !3& )a -/. %H%-# Col )a33-/.-H03 H%- This water is shown as ,H%- in chemical analyses. 4ater absorbed as moisture on minerals shown as *H%-. REPRESENTATION OF MINERAL FORMULA Mineral formulas are e5pressed as elemental cation*anion pairs or sometimes are bro1en down to simple compounds such as o5ides. C'l )a)-3 )a-.)-% Dol )aM".)-30% )a-.M"-.%)-% 53' 6l% i-( 6l%-3# i-% Ort 76l i3-' 7%-.6l%-3.8 i-% Ol# .M"Fe0% i-/ M"-.Fe-. i-% A&' )a(.9-/03.F#)l#-H0 $)a-.)a.F#)l#-H0%.39%-( M't Fe3-/ Fe-.Fe%-3 or Fe%,-.Fe3,%-3 CALCULATION OF CHEMICAL FORMULA OF MINERALS 6 :uantitative chemical analysis of a mineral provides the basic information for the atomic or molecular formula of the mineral. 2t is "iven as 6t7 in terms of elements or o5ides and outlines a listin" of what elements or o5ides are present. 6 :uantitative chemical analysis should add up close 100;1<.

Ste&s #n the $'l$ul't#onA From Element'l An'l3s#s ". )ompare the ma5imum wt< for possible anion .=0 and name the ma>or mineral "roup as ulphide ulphate ilicate )arbonate 9hosphate etc. /. )onsider and "roup the cations accordin" to their valency as +a,# 7, M"%,#Fe%,#?n%, 6l3,# Fe3, i/,# Ti/, etc. 3ecause they may replace each other in the formula. 3. @ivide wt< values by atomic wei"ht "iven and mutiply by 1000 to avoid fractions. 8. -mit trace and minor elements or o5ides. 9. 6dd atomic proportions of possible substitutions# i.e. ?n Fe. ,. @etermine atomic proportions as appro5imate whole numbers. :. 4rite chemical formula cations first anions last# .?n#Fe0 . ;. 2f re:uired recalculate atomic percenta"e of cations in the formula. <. 4rite chemical formula cations percenta"es first anion last# .?n'A# Fe130 . !5ample 1. Fe Mn ?n )d 2n C )t7 1'.%( %.88 //.8A 0.%' 0.01 33.(A $$.// Atom#$ )e#*hts ((.'( (/.$/ 8(.3' 11%./0 11/.'% 3%.0A Atom#$ Pro&ort#ons = ">>> 3%A /' 8'3 1080 % 0.1 .omitted0 10/A 10/A Atom#$ R't#os

B1

B1

It #s ' sul&h#0e !ener'l 2ormul' (?n@Fe@Mn@C0)S N'me SPHALERITE 2f atomic percenta"es of cations are re:uired: Fe Fe 3%A Mn 30.' Mn 0.% /' ?n /.( ?n 8'3 )d % 8/./ Total 1080 Factor l00D1080E69 )d

+ow the formula is .?n8/./Fe30.'Mn/.()d0.%0 1 From O=#0e An'l3s#s teps " A / 're s'me 3. @ivide wt< values by molecular wei"hts "iven and multiply by 1000 to avoid fractions to obtain Molecular 9roportions. teps 8 to < are same a"ain but remember we are dealin" with molecular proportions of o5ides.

!5ample %. i-% Ti-% 6l%-3 Fe%-3 FeMnM"C )t7 3/.$8 0.0% 0.1% 0.03 38.AA 0.(% %A.0/ $$./8 Mole$ul'r )e#*hts Mole$ul'r Pro&ort#ons = ">>> 80.0$ ('% ('% A$.$0 0.3 .omitted0 101.$8 1 .omitted0 1($.A0 0.% .omitted0 A1.'( (1% A0.$/ A 11$0 /0.31 8A1 Mole$ul'r R't#os B1

B%

It #s ' s#l#$'te !ener'l 2ormul' /(M*@Fe@Mn)O S#O/ or (M*@Fe@Mn)/S#O8 N'me OLI.INE 2f atomic percenta"es of cations are re:uired: Fe- (1% Fe- /3.0 Mn- A Mn- 0.8 M"- 8A1 M"- (8./ Total 11$0 Factor 100D1 1F-EM9

+ow the formula is .M"(8./Fe/3.0Mn0.80% i-/ or Fos9:F'383 C For An'l3s#s o2 M#ner'l M#=tures teps " to < are the same a"ain. 3ut we have to ma1e some assumptions about the number of minerals and about whether their bein" pure end members. 2f there are same elements present in different mineral phases than the calculations is very difficult# if not impossible. !5ample 3 9b ?n )u Fe 2n C )t7 /./3 11.(8 %8.(/ %3.'/ 0.01 33.(A 100.(/ Atom#$ )e#*hts %0A.%0 8(.3' 83.(( ((.'( 11/.'% 3%.0A Atom#$ Pro&ort#ons = ">>> %1 1AA /1' /%A 0.1 .omitted0 108( *%(G10// *1AAG'8A .C&30. Atom#$ R't#os

B1 B1 B%

Formulas of the minerals are 9b .!'l0# ?n .S&h0 and )uFe 2f percenta"es of minerals are re:uired 9b ?n %1E% 1AAE% /% 3(/ %.0< 18.'<

)uFe

1A1% '1.%< %10' 100#0 SOLID SOLUTION or ISOMORPHISM Henerally minerals are not pure substances. There is e5tensive variation in chemical composition. This variation is result of su%st#tut#on. 2n a sol#0 solut#on# specific atomic sites of the mineral structure are occupied in variable proportions by different atoms. This is controllcd by thc .10 siIe of the atoms or ions .J1(< in siIe difference0# .%0 valency of the substitutin" ions .electric char"e must be balanced# hence $ou&le0 su%st#tut#on i/,6l3,,+a,0# .30 at hi"h temperatures due to thermal vibrations atomic sites are lar"er and therefore "reater possibility for substitution. There are three types of solid solutions:
%

rest

Su%st#tut#on'l Sol#0 Solut#on S#m&le C't#on#$ or An#on#$ su%st#tut#ons. 2t occurs in most mineral structures. !". 3r* anion substitution of )l in S3lvite .7)l0 crystal structure. 5(CI@1r) Com&lete 1#n'r3 Sol#0 Solut#on Ser#es 2n Ol# .M"#Fe0% i-/ structure M"%,Fe%, substitution is complete. En0 mem%ers are Fos M"% i-/ and F'3 Fe% i-/ (FI! 3 3) Com&lete m#s$#%#l#t3 e5ists between these end members. !arly formed Ol# crystals are Fos rich. 6s T falls they react with the silicate melt and become richer in F'3 component by ta1in" Fe%, ions into their crystal structure. 2f coolin" is rapid that prevents early formed portion of crystal to react with the li:uid# 4on#n* may form with Fos rich portion occurrin" in the core of the Ioned Ol# crystal (FI! 3 8). 2n Pl'* series there is complete but coupled substitution. !nd members are Al% +a6l i3-' and Ano )a6l% i%-'. @urin" coupled substitution )a%,,6l3, +a,, i/, (FI! 3 9) However# Fel0 "roup consists of two solid solution series. 2n ABFel0 series at hi"h temperatures there is complete solid solution. 3ut at low temperatures there is only limited solid solution (FI! 3 ,). !nd members are Ort 76l i3-' and Al% +a6l i3-' where +a,7,. Therefore there e5ists a m#s$#%#l#t3 *'&. Interst#t#'l Sol#0 Solut#on 2f holes or voids e5ist in the crystal structure# lar"e ions or molecules can enter into the crystal structure formin" interstitial substitution. 2n 1er 3e36l% i801' crystals neutral H%-# )-% molecules or lar"e 7,# Kb,# )s, ions can enters into lar"e holes located between silicate rin"s (FI! 3 :). 2n the case of entrance of neutral H%-# )-% molecules no char"e balance is needed# otherwise coupled substitutions occur i/,3e%,,%K, or i/,6l3,,K, where K, represents monovalent lar"e ions which are to be accommodated. Om#ss#on Sol#0 Solut#on 4hen a hi"hly char"ed cation replaces two or more cations in a crystal structure a vacancy or omission occurs in one of the atomic sites. !".# 9b in Am'Ionite 76l i3-' which is a polymorph of 5BFel0. Here# , , 7 ,7 9b%,, creatin" a vacancy in the crystal structure. 6nother e5ample is P3rrhotite Fe.l*50 . Here 5G0*0.% and the mineral said to have a 0e2e$t stru$ture. 2t is e5plained as Fe%,,Fe%,,Fe%,Fe3,,Fe3,, (FI! 3 ;).

)ommon solid solution series: 1. 2sometric .)ubic0 system: S&#nel "roup# !'rnet "roup# %. Tetra"onal system: Rutile "roup# S$heelite "roup# 3. He5a"onal system: A&'tite "roup# Corundum "roup# /. -rthorhombic system: Ar'"onite "roup# 1'rite "roup# (. Monoclinic system: P3= "roup# Am& "roup# 8. Triclinic systemL Fel0 "roup. 2n solid solution series some physical properties of the mineral "roups show more or less linear variation from one end member to another (FI! 3 <). 1. Meltin" point# boilin" point# crystalliIation T# %. pecific "ravity# 3. Hardness# /. )ell dimensions# (. -ptical properties RI# birefrin"ence# e5tinction an"le etc. ECSOLUTION or UNMICIN! This process is the opposite of solid solution. !5solution is due to the substitution of atoms or ions havin" different siIe. Henerally# at lower T enlar"ed atomic sites at hi"h T in the mineral structure# becomes smaller. Hence# lar"er ions present in the structure leads to chemical disorder. Therefore at hi"h T initially homo"eneous solid solution separates into two distinct minerals havin" different chemical composition. The bul1 composition remains same. E=solut#on l'mell'e that separates from the host crystal are "enerally crystallo"raphically oriented (FI! 3 ">) !". 2n ABFel0 Al% lamellae e5solved in Ort9!KTH2T! (FI! 3 "")- Ort lamellae solved in Al%6+T29!KTH2T!. )a rich ClBP3= havin" )a poor OBP3= lamellae# or vise versa. PSEUDOMORPHISM 2f a crystal of a mineral is altered so that the internal structure or chemical composition is chan"ed but the e5ternal form is preserved it is called a pseudomorph. !". L#m Fe-.-H nH%- after P3t Fe %. )rystal form is that of P3t but composition is altered to amorphous L#m. 1. Loss of a constituent Cu&rite )u%-+ative Cu %. Hain of a constituent Anhydrite )a -/!3& )a -/ %H%3. 9artial e5chan"e of constituents Limonite Fe-.-H nH%-!oethite Fe-.-H /. )omplete e5chan"e of constituents Flu )aF%Du' i-%L ilicified wood where or"anic compounds are replaced by silica (FI! 3 "/)