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Oksidacijsko stanje

število, ki opisuje stopnjo oksidiranosti atoma v kemični spojini; hipotetični naboj, ki bi ga imel atom, če bi bile vse vezi z atomi različnih elementov popolnoma ionske From Wikipedia, the free encyclopedia

Oksidacijsko stanje
Računanje formalnega oksidacijskega stanjaRačunanje oksidacijskega stanja iz strukturne formuleRačunanje brez strukturne formuleElementi z več oksidacijskimi stanjiUlomljena oksidacijska stanjaOksidacijsko številoSeznam oksidacijskih stanj elementovZgodovinaViriSklici

Oksidacijsko stanje je v kemiji indikator stopnje oksidacije atoma ali kemijske spojine. Formalno oksidacijsko stanje je hipotetični naboj, ki bi ga imel atom, če bi bile vse njegove vezi z drugimi atomi 100 % ionske. Oksidacijska stanja so izražena s pozitivnimi ali negativnimi celimi števili ali z ničlo (0).

Naraščanje oksidacijskega stanja med kemijsko reakcijo imenujemo oksidacija, padanje oksidacijskega stanja pa redukcijo. V takšnih reakcijah pride do prenosa elektronov: sprejemanje elektronov je redukcija, oddajanje elektronov pa oksidacija. Elementi imajo oksidacijsko število nič (0).

Definicija oksidacijskega stanja po pravilih IUPAC:[1]

"Oksidacijsko stanje: merilo stopnje oksidacije atoma ali spojine. Oksidacijsko stanje je definirano kot naboj, ki bi ga imel atom, če bi elektrone šteli po naslednjih pravilih: (1) oksidacijsko stanje prostega (nevezanega) elementa je enako nič; (2) oksidacijsko stanje enostavnega (enoatomskega) iona je enako neto naboju tega iona; (3) vodik in kisik imata v večini spojin oksidacijski stanji +1 (vodik) oziroma -2 (kisik); izjeme so kovinski hidridi, na primer LiH, v katerem ima vodik oksidacijsko stanje -1, in peroksidi, na primer H2O2, v katerih ima kisik oksidacijsko stanje -1; (4) algebraična vsota oksidacijskih stanj vseh atomov v nevtralni molekuli je enaka nič (0); algebraična vsota nabojev vseh atomov v ionu je enaka naboju iona. Primeri: oksidacijska stanja žvepla v spojinah H2S, S8 (elementarno žveplo), SO2, SO3 in H2SO4 so -2, 0, +4, +6 in +6. Višje oksidacijsko stanje nekega atoma pomeni višjo stopnjo oksidacije, nižje oksidacijsko stanje pa pomeni višjo stopnjo redukcije."

Oksidacijsko stanje atoma ali spojine lahko izračunamo na dva načina. Prvi način se uporablja za molekule, ki so prikazane z Lewisovo (strukturno) formulo, ki se pogosto uporablja za zapis organskih spojin. Drugi način se uporablja za preproste spojine, ki ne potrebujejo strukturne formule.

Ponovno je treba poudariti, da oksidacijsko stanje atoma ne predstavlja njegovega realnega naboja, kar je še posebno res pri visokih oksidacijskih stanjih. Ionizacijska energija, ki je potrebna za tvorbo multiplega pozitivnega iona je namreč mnogo večja od energije, ki je na razpolago v kemijskih reakcijah. Pripisovanje elektronov posameznim atomom pri računanju oksidacijskega stanja je čisti formalizem, ki pa je zelo uporaben za razumevanje mnogih kemijskih reakcij.

Računanje oksidacijskega stanja iz strukturne formule

Za molekule z znano strukturno formulo lahko oksidacijska stanja atomov izračunamo z računanjem razlike med številom valenčnih elektronov, ki bi jih imel nevtralen atom elementa in številom elektronov, ki mu »pripadajo« v Lewisovi strukturi. Pri računanju oksidacijskega stanja upoštevamo naslednje zakonitosti: (1) vezni elektroni med atomi različnih elementov pripadejo bolj elektronegativnemu atomu, (2) vezne elektrone med dvema enakima atomoma si atoma razdelita in (3) elektroni iz neveznih elektronskih parov pripadajo tistemu elementu, ki jim ima.

Primer: etanojska (ocetna) kislina

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V metilni skupini (-CH3) ima ogljikov atom 6 valenčnih elektronov iz vezi s tremi vodikovimi atomi, ker je bolj elektronegativen od vodika, en elektron pa mu pripada iz elektronskega para vezi C-C. Ogljik ima torej 7 valenčnih elektronov. Nevtralni ogljikov atom bi imel 4 valenčne elektrone, ker je v 4. (oziroma 14.) skupini periodnega sistema elementov. Razlika 4 - 7 = -3 je oksidacijsko stanje tega ogljikovega atoma. Izračun seveda sloni na predpostavki, da so vse vezi 100 % ionske, kar seveda ni res. Ogljikov »ion« bi tem primeru zapisali kot C3-.

Če na enak način izračunamo oskidacijsko stanje ogljikovega atoma v karboksilni skupini (-COOH), dobimo rezultat +3, ker mu pripada en elektron iz vezi C-C, ostali vezni elektroni pa pripadejo bolj elektronegativnemu kisiku. Oba kisikova atoma imata oksidacijsko stanje -2, ker imata po 8 elektronov: 4 iz vezi z ogljikom oziroma ogljikom in vodikom (ker sta bolj elektro negativna) in 4 svoje nevezne elektrone, nevtralni kisik pa bi jih imel 6. Vodik ima oksidacijsko število vedno enako +1, ker so vsi elementi, s katerimi se veže, bolj elektronegativni od njega samega.

Oksidacijska stanja so zelo uporabna pri uravnovešanju redoks reakcij, v katerih mora biti število prejetih in oddanih elektronov enako. Če vzamemo za primer oksidacijo etanala (acetaldehida) s Tollensovim reagentom v etanojsko (ocetno) kislino, vidimo, da je karbonilni C atom spremenil svoje oksidacijsko stanje iz +1 v +3 (oksidacija). Na ta račun sta se dva atoma Ag reducirala iz Ag+ v Ag0:

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Računanje brez strukturne formule

Algebaična vsota oksidacijskih stanj vseh atomov v nevtralni molekuli mora biti enaka nič, algebraična vsota oksidacijskih stanj v ionu pa mora biti enaka naboju iona. To dejstvo in dejstvo, da imajo nekateri elementi skoraj vedno določena oksidacijska stanja, omogočajo enostaven izračun oksidacijskih stanj atomov v enostavnih spojinah. Za izračunavanje upoštevamo naslednjih nekaj pravil:

  • Fluor ima v vseh spojinah oksidacijsko stanje -1, ker je najbolj elektronegativen od vseh reaktivnih elementov.
  • Vodik ima oksidacijsko stanje +1, razen v spojinah z bolj elektropozitivnimi elementi, na primer natrijem, aluminijem in borom v spojinah kot so NaH, NaBH4, LiAlH4 (hidridi), v katerih ima oksidacijsko stanje -1.
  • Kisik ima oksidacijsko stanje -2, razen v peroksidih (-1), superoksidih (-½), ozonidih (-⅓) in kisikovih fluoridih OF2 in difluoridid O2F4 (+1).
  • Alkalijske kovine iz prve skupine periodnega sistema elementov imajo v vseh spojinah, razen v alkalidih, oksidacijsko stanje +1.
  • Kovine iz druge skupine periodnega sistema elementov imajo v (skoraj) vseh spojinah oksidacijsko stanje +2.
  • Halogeni elementi, razen fluora, imajo oksidacijsko stanje -1. Izjema so spojine s kisikom, dušikom in drugimi halogenimi elementi.

Primer: v spojini Cr(OH)3 ima kisik oksidacijsko stanje -2 (v spojini ni niti fluora niti vezi O-O), vodik pa +1 (vezan na elektronegativni kisik). Tri hidroksidne skupine imajo skupaj naboj 3x(-2+1) = -3, torej ima krom oksdacijsko stanje +3.

Večina elementov ima več kot eno oksidacijsko stanje. Ogljik ima devet oksidacijskih stanj:

1. –4: CH4

2. –3: C2H6

3. –2: CH3F

4. –1: C2H2

5. 0: CH2F2

6. +1: C2H2F4

7. +2: CHF3

8. +3: C2F6

9. +4: CF4

Kisik ima osem oksidacijskih stanj:

1. -2: v večini oksidov, na primer ZnO, CO2, H2O

2. -1: v vseh peroksidih

3. -½: v superoksidih, na primer v KO2

4. -⅓: v ozonidih, na primer RbO3

5. 0: O2

6. +½: kot dioksigenil, na primer v O2+[AsF6]-

7. +1: O2F2

8. +2: OF2

Formalna oksidacijska stanja atomov v Lewisovi zgradbi bi morala biti vedno cela števila. Osidacijska stanja se kljub temu pogosto izražajo z ulomki, ki predstavljajo povprečno oksidacijsko stanje atomov in drugih struktur. Primer: v KO2 ima kisik povprečno oksidacijsko stanje -½, ker ima en kisikov atom stanje 0, drugi pa -1. V nekaterih primerih sta zaradi resonance oba atoma lahko enakovredna. V takih primerih enostavna Lewisova strukturna formula ni uporabna, ker je za tak prikaz potrebnih več struktur.

Izraza osidacijsko stanje in oksidacijsko število sta pogosto zamenjljiva, če pa smo zelo natančni, se oksidacijsko število uporablja v kemiji kompleksnih (koordinacijskih) spojin in ima rahlo drugačen pomen. V kemiji kompleksov so namreč pravila za štetje elektronov drugačna: vsak elektron pripada ligandu skladno z njegovo elektronegativnostjo. Oksidacijska števila so običajno zapisana z rimskimi številkami, medtem ko so oksidacijska stanja zapisana z arabskimi številkami.

To je seznam znanih oksidacijskih stanje elementov, brez ulomljenih oksidacijskih stanj. Najpogostejše stanje je zapisano poudarjeno. Tabela temelji na Greenwood in Earnshaw,[2] z dodanimi komentarji. Vsak element obstaja v oksidacijskem stanju 0, medtem ko je čisti neioniziran element v katerikoli fazi. Stolpec oksidacijskega stanja 0 prikazuje le elemente za katere je znano da v spojinah obstajajo v oksidacijskem stanju 0.

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Več informacij Element, Negativna stanja ...
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Oksidacijska stanja elementov
Element Negativna stanja Pozitivna stanja Skupina Opombe
−5 −4 −3 −2 −1 0 +1 +2 +3 +4 +5 +6 +7 +8 +9
Z
1 vodik H −1 !−1 1 !+1 1
2 helij He 18
3 litij Li 1 !+1 1 [3]
4 berilij Be 0 +1 2 !+2 2 [4][5]
5 bor B −5 −1 0 +1 +2 3 !+3 13 [6][7][8]
6 ogljik C −4 !−4 −3 !−3 −2 !−2 −1 !−1 0 !0 1 !+1 2 !+2 3 !+3 4 !+4 14
7 dušik N −3 !−3 −2 −1 +1 +2 3 !+3 +4 5 !+5 15
8 kisik O −2 !−2 −1 0 +1 +2 16
9 fluor F −1 !−1 17
10 neon Ne 18
11 natrij Na −1 1 !+1 1 [3]
12 magnezij Mg +1 2 !+2 2 [9]
13 aluminij Al −2 −1 +1 +2 3 !+3 13 [10][11][12]
14 silicij Si −4 !−4 −3 −2 −1 0 +1 +2 +3 4 !+4 14 [13]
15 fosfor P −3 !−3 −2 −1 0 +1 +2 3 !+3 +4 5 !+5 15 [14]
16 žveplo S −2 !−2 −1 0 +1 2 !+2 +3 4 !+4 +5 6 !+6 16
17 klor Cl −1 !−1 1 !+1 +2 3 !+3 +4 5 !+5 +6 7 !+7 17 [15]
18 argon Ar 0 !0 18 [16]
19 kalij K −1 1 !+1 1 [3]
20 kalcij Ca +1 2 !+2 2 [17]
21 skandij Sc 0 +1 +2 3 !+3 3 [18][19][20]
22 titan Ti −2 −1 0 +1 +2 +3 4 !+4 4 [21][22][23][24]
23 vanadij V −3 −1 0 +1 +2 +3 +4 5 !+5 5 [22]
24 krom Cr −4 −2 −1 0 +1 +2 3 !+3 +4 +5 6 !+6 6 [22]
25 mangan Mn −3 −2 −1 0 +1 2 !+2 +3 4 !+4 +5 +6 7 !+7 7
26 železo Fe −4 −2 −1 0 +1 2 !+2 3 !+3 +4 +5 6 !+6 +7 8 [25][26][27]
27 kobalt Co −3 −1 0 +1 2 !+2 3 !+3 +4 +5 9 [22]
28 nikelj Ni −2 −1 0 +1 2 !+2 +3 +4 10 [28]
29 baker Cu −2 0 1 !+1 2 !+2 +3 +4 11 [27][29]
30 cink Zn −2 0 +1 2 !+2 12 [27][30][31]
31 galij Ga −5 −4 −3 −2 −1 +1 +2 3 !+3 13 [11][32][33]
32 germanij Ge −4 !−4 −3 −2 −1 0 +1 2 !+2 +3 4 !+4 14 [34][13]
33 arzen As −3 !−3 −2 −1 0 +1 +2 3 !+3 +4 5 !+5 15 [11][35][36][37]
34 selen Se −2 !−2 −1 +1 2 !+2 +3 4 !+4 +5 6 !+6 16 [38][39][40][41]
35 brom Br −1 !−1 1 !+1 3 !+3 +4 5 !+5 +7 17
36 kripton Kr 0 !0 +1 +2 18
37 rubidij Rb −1 1 !+1 1 [3]
38 stroncij Sr +1 2 !+2 2 [42]
39 itrij Y 0 +1 +2 3 !+3 3 [43][44][45]
40 cirkonij Zr −2 0 +1 +2 +3 4 !+4 4 [22][46][47]
41 niobij Nb −3 −1 0 +1 +2 +3 +4 5 !+5 5 [22][48][49]
42 molibden Mo −4 −2 −1 0 +1 +2 +3 4 !+4 +5 6 !+6 6 [22]
43 tehnecij Tc −3 −1 0 +1 +2 +3 4 !+4 +5 +6 7 !+7 7
44 rutenij Ru −4 −2 0 +1 +2 3 !+3 4 !+4 +5 +6 +7 +8 8 [22][27]
45 rodij Rh −3 −1 0 +1 +2 3 !+3 +4 +5 +6 9 [22][50]
46 paladij Pd 0 !0 +1 2 !+2 +3 4 !+4 10 [51][52]
47 srebro Ag −2 −1 1 !+1 +2 +3 11 [27][53]
48 kadmij Cd −2 +1 2 !+2 12 [27][54]
49 indij In −5 −2 −1 +1 +2 3 !+3 13 [11][55][56]
50 kositer Sn −4 !−4 −3 −2 −1 0 +1 2 !+2 +3 4 !+4 14 [11][57][58][13]
51 antimon Sb −3 !−3 −2 −1 0 +1 +2 3 !+3 +4 5 !+5 15 [11][59][60][61][62]
52 telur Te −2 !−2 −1 +1 2 !+2 +3 4 !+4 +5 6 !+6 16 [11][63][64][65]
53 jod I −1 !−1 1 !+1 3 !+3 +4 5 !+5 +6 7 !+7 17 [66][67]
54 ksenon Xe 0 !0 +1 +2 +4 +6 +8 18 [68][69][70]
55 cezij Cs −1 1 !+1 1 [3]
56 barij Ba +1 2 !+2 2 [71]
57 lantan La 0 +1 +2 3 !+3 n/a [43][72]
58 cerij Ce +2 3 !+3 4 !+4 n/a
59 prazeodim Pr 0 +1 +2 3 !+3 +4 +5 n/a [43][73][74][75]
60 neodim Nd 0 +2 3 !+3 +4 n/a [43][76]
61 prometij Pm +2 3 !+3 n/a [77]
62 samarij Sm 0 +2 3 !+3 n/a [43]
63 evropij Eu 0 2 !+2 3 !+3 n/a [43]
64 gadolinij Gd 0 +1 +2 3 !+3 n/a [43]
65 terbij Tb 0 +1 +2 3 !+3 +4 n/a [43][77]
66 disprozij Dy 0 +2 3 !+3 +4 n/a [43][78]
67 holmij Ho 0 +2 3 !+3 n/a [43][77]
68 erbij Er 0 +2 3 !+3 n/a [43][77]
69 tulij Tm 0 +2 3 !+3 n/a [43]
70 iterbij Yb 0 +2 3 !+3 n/a [43]
71 lutecij Lu 0 +2 3 !+3 3 [43][77]
72 hafnij Hf −2 0 +1 +2 +3 4 !+4 4 [22][47][79]
73 tantal Ta −3 −1 0 +1 +2 +3 +4 5 !+5 5 [22][49]
74 volfram W −4 −2 −1 0 +1 +2 +3 4 !+4 +5 6 !+6 6 [22]
75 renij Re −3 −1 0 +1 +2 +3 4 !+4 +5 +6 +7 7
76 osmij Os −4 −2 −1 0 +1 +2 +3 4 !+4 +5 +6 +7 +8 8 [27][80]
77 iridij Ir −3 −1 0 +1 +2 3 !+3 4 !+4 +5 +6 +7 +8 +9 9 [81][82][83][84]
78 platina Pt −3 −2 −1 0 +1 2 !+2 +3 4 !+4 +5 +6 10 [27][85][86]
79 zlato Au −3 −2 −1 0 1 !+1 +2 3 !+3 +5 11 [27][87]
80 živo srebro Hg −2 1 !+1 2 !+2 12 [27][88]
81 talij Tl −5 −2 −1 1 !+1 +2 3 !+3 13 [11][89][90][91]
82 svinec Pb −4 −2 −1 +1 2 !+2 +3 4 !+4 14 [11][92][93]
83 bizmut Bi −3 −2 −1 +1 +2 3 !+3 +4 +5 15 [94][95][96][97]
84 polonij Po −2 !−2 2 !+2 4 !+4 +5 +6 16 [98]
85 astat At −1 !−1 1 !+1 +3 +5 +7 17
86 radon Rn 2 !+2 +6 18 [99][100][101]
87 francij Fr 1 !+1 1
88 radij Ra 2 !+2 2
89 aktinij Ac 3 !+3 n/a
90 torij Th +1 +2 +3 4 !+4 n/a [102][103]
91 protaktinij Pa +3 +4 5 !+5 n/a
92 uran U +1 +2 +3 4 !+4 +5 6 !+6 n/a [104][105]
93 neptunij Np +2 +3 +4 5 !+5 +6 +7 n/a [106]
94 plutonij Pu +2 +3 4 !+4 +5 +6 +7 +8 n/a [107][108]
95 americij Am +2 3 !+3 +4 +5 +6 +7 n/a [109]
96 kirij Cm 3 !+3 +4 +5 +6 n/a [110][111][112][113]
97 berkelij Bk +2 3 !+3 +4 +5 n/a [110][111][114][115][116]
98 kalifornij Cf +2 3 !+3 +4 +5 n/a [110][111]
99 ajnštajnij Es +2 3 !+3 +4 n/a [117]
100 fermij Fm +2 3 !+3 n/a
101 mendelevij Md +2 3 !+3 n/a
102 nobelij No 2 !+2 +3 n/a
103 lavrencij Lr 3 !+3 3
104 raderfordij Rf 4 !+4 4
105 dubnij Db 5 !+5 5 [118]
106 siborgij Sg 0 6 !+6 6 [119][120]
107 borij Bh 7 !+7 7 [121]
108 hasij Hs 8 !+8 8 [122]
109 majtnerij Mt 9
110 darmštatij Ds 10
111 rentgenij Rg 11
112 kopernicij Cn 2 !+2 12 [123]
113 nihonij Nh 13
114 flerovij Fl 14
115 moskovij Mc 15
116 livermorij Lv 16
117 tenes Ts 17
118 oganeson Og 18
Zapri

Koncept oksidacijskih stanj, kot ga poznamo danes, je vpeljal W.M. Latimer leta 1938. Oksidacijo kot tako je prvi študiral Antoine Lavoisier (1743–1794), ki je nanjo gledal kot na reakcijo elementov s kisikom in je bil prepričan, da kemijske vezi v vseh soleh temeljijo na kisiku.[124]

  • Brady, J.E., Holum, J.R.,Chemistry, John Wiley & Sons, 1993, ISBN 0-471-59979-4
  • Filipović I., Lipanović, S.: Opća i anorganska kemija, Školska knjiga, 1973.
  1. [1]
    IUPAC Gold Book
  2. [2]
    Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2. izd.). Butterworth-Heinemann. str. 27–28. ISBN 978-0-08-037941-8.
  3. [3]
    Na(−1), K(−1), Rb(−1), and Cs(−1) are known in alkalides; the table by Greenwood and Earnshaw shows −1 only for Na and also erroneously for Li; no lithides are described.
  4. [4]
    Be(0) has been observed; see »Beryllium(0) Complex Found«. Chemistry Europe. 13. junij 2016.
  5. [5]
    Be(I) has been observed in beryllium monohydride (BeH); see Shayesteh, A.; Tereszchuk, K.; Bernath, P. F.; Colin, R. (2003). »Infrared Emission Spectra of BeH and BeD« (PDF). J. Chem. Phys. 118 (3): 1158. Bibcode:2003JChPh.118.1158S. doi:10.1063/1.1528606. Arhivirano iz prvotnega spletišča (PDF) dne 2. decembra 2007. Pridobljeno 10. decembra 2007. and in [(CAAC)2Be]+• [CAAC = cyclic (alkyl)(amino)carbene], see Wang, Guocang; Walley, Jacob E.; Dickie, Diane E.; Pan, Sudip; Frenking, Gernot; Gilliard Jr., Robert G. (2020). »A Stable, Crystalline Beryllium Radical Cation«. J. Am. Chem. Soc. 142 (10): 4560–4. doi:10.1021/jacs.9b13777. Pridobljeno 17. novembra 2020.
  6. [6]
    B(−5) has been observed in Al3BC, see Schroeder, Melanie. »Eigenschaften von borreichen Boriden und Scandium-Aluminium-Oxid-Carbiden« (v nemščini). str. 139.
  7. [7]
    B(−1) has been observed in magnesium diboride (MgB2), see Keeler, James; Wothers, Peter (2014). Chemical Structure and Reactivity: An Integrated Approach. Oxford University Press. ISBN 9780199604135.
  8. [8]
    B(0) has been observed in diborynes, see Braunschweig, H.; Dewhurst, R. D.; Hammond, K.; Mies, J.; Radacki, K.; Vargas, A. (2012). »Ambient-Temperature Isolation of a Compound with a Boron-Boron Triple Bond«. Science. 336 (6087): 1420–2. Bibcode:2012Sci...336.1420B. doi:10.1126/science.1221138. PMID 22700924.
  9. [9]
    Low valent magnesium compounds with Mg(I) have been obtained using bulky ligands; see Green, S. P.; Jones C.; Stasch A. (december 2007). »Stable Magnesium(I) Compounds with Mg-Mg Bonds«. Science. 318 (5857): 1754–1757. Bibcode:2007Sci...318.1754G. doi:10.1126/science.1150856. PMID 17991827.{{navedi časopis}}: Vzdrževanje CS1: samodejni prevod datuma (povezava)
  10. [10]
    Al(II) has been observed in aluminium(II) oxide (AlO); see Tyte, D.C. (1964). »Red (B2Π–A2σ) Band System of Aluminium Monoxide«. Nature. 202 (4930): 383–384. Bibcode:1964Natur.202..383T. doi:10.1038/202383a0, and in dialanes (R2Al—AlR2); see Uhl, Werner (2004). »Organoelement Compounds Possessing Al—Al, Ga—Ga, In—In, and Tl—Tl Single Bonds«. Advances in Organometallic Chemistry. 51: 53–108. doi:10.1016/S0065-3055(03)51002-4.
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    Negative oxidation states of p-block metals (Al, Ga, In, Sn, Tl, Pb, Bi, Po) and metalloids (Si, Ge, As, Sb, Te, At) may occur in Zintl phases, see: Riedel, Erwin, ur. (2007). Moderne Anorganische Chemie (v nemščini). str. 259, and »Vorlesung Intermetallische Phasen § 6.2 Binäre Zintl-Phasen« (v nemščini).
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