Chapter l0

The photosynthetic process

l0.l lntroduction
Pho(osynthes,s is rhe makins (synrhesis) of orsanic srrucrures and chemical
enersy srores by rhe ac0on of sol:r radiarion (phoro). Ii ,s by far rhe
mosr imporranr renewable energy process, because livine orsan'snN irc
made from material fixed by phorosynrhesrs, and our acr'v'ries rely on
oxygen in which the solar energy rs mosdy stored. For ;nsrance. hnm.n
merabolism continuously releases about 150 W per person from food. Thus,
both rhe marenals and rhe energy for all life are made available;n sascs
crrculrting rn the Earrh's atmosphere, namely carbon dioxide and orygen.
5adly, despite photosynrhesis beinS a physically induced process and thc
drrvrng funcrion of oarural engineering, rhe subjecr rs missing from mosr
physics and engineering texG. This chaprer tries ro recnfy rhis omission
by descr;bing a cheap process rhar provides abundant srored energy an
engrneefs dream, bur a natural phenomenon.
The contifluous phorosynrheric outpur flux on rh Eafth is abour 0.9:
10rav (i.e- abour 15kV per person; rhe power ourpur of 100000 large
nuclear power !tarion!). This chapter discovers how rhe preess occurs
wtrhin molecules and celh, and how evenrually ir may be urilised at rhese
levels. Energy supply from plant and animal materials, bromass, is drscussed
rn Chrprer 1l Solar radisrion incrdenr oD green planrs and orher phoro
synrheric organisms relares ro lvo main effects: (1) remperature conrrot i(,r
chem,cal reaclons ro proceed, espcially in laves, and (2)phoro excnarron
of electrons for rhe pnrduction of oxygen and carbon srructural materrat. It
rs so rmporr,n o majnrain leaf remperarure in rhe correcr range rhat sonre
solar radiario. is reflected or rransmirred, rarher rhan absorbed (rhjs is why
leales are seldom black). The enersy processes in phorosynrhesis depcnd on
nrc photons (enersy packers) of ihe dar radiarion, tabetted .r,', where , is
Plancl s consranr and r is rhe frequency of rhe radi?rion. fhe o.gani( mare,
rral produced rs mainly carbohydrate, wrrh carbon rn r nredium posrtion
of ox'darion and reducrion (e.s. slucose, C6HE06). Ii ih,s (dry) nrareriat ,r
burnt in oxygen, rhe hear releas.d rs abour t5MJkg-r (4.seV pcr.arboD
amnr, a60 kJ per mole or carboD). The fix.rion of one carl,on arom fronr
 10 1 1ntrod (ti o 325

armospheric CO, to carbohydrare procceds by a series of stages m green

plants, includrg algae:

Reacrons in lisht, in wh,ch phorons produce prorons fronr HrO, wirh

Or as an imponanr by'product, and elecrrons are excired rn rwo srages
ro produce srrons reducins chemicak.
Reacrions not requirins lishr (called dark reactions),,n whrch rhese
reducins chemicals reduce CO, ro carbohydrares, proteins and fars.

Combining both the lighr and rhe dark reactions givcs an overall reacrion,
neglecring .rany inrernediare srcps:

C 2 O JoLq+ 0 (101)
0

shdr produr. nJ\e "bou a r.\ Fr , rrhnn rr,,m moa enrhalpr

rhe
,enersi producrrn porenrJl, rhan,h, rnrtral nraterral brurrr+ of thr absorp-
tior of ar leasr eight photons. Hcre [CH,o] represenrs J basic unrt of
czrbohydratc, r rhe reaction Ior sucrose production is

l2COr+24H,O lq- 12Or rCrllrOI ilJHrL) (102)

In rhese equanons, the oxygen atoms iniraliy in COl an<J HlO are dstin-
guished, rhe lancr being shown wrth a dots over the O.
Most srudies of phorosysrhesrs depend on biochemical analysrs consider
rng the many complex chemical processcs involved. This chapter, however,
will emphas,se rhe physical procesles, and will relate ro the branch ofspec-
rroscopy called photophysics. There will also be inreresong similarrries and
.omparisons wrrh phorovohaic devices (Chapter 7). we,hall proceed in

I rhe trophrc level (Fi8ure 10.1)

2 lhe planr level (Fisure 10.2)
I The molecular level (Fisure 10.3): this rs a complex system, whrch will
be srudied in Scction 10.6.

Tle.e is exrcnsrve variety rn all aspecrs of photosynrhess, froo the scale

of plants down to molecular level. lr musi not be assumed th.t any one
!ysrem is as str.rshtforward as described rn thr chaprer, whrch concertrates
on rhe general phystcal principles. However, the end resulr rs lhat e ergv
{rom rhe Sun is (ored in srable chenrrols for later use a prilciple goal of
renewable energy technology, yet happcning all around us.
 326 The photoslnrhe!i< process

(P ,g&
7 tttfri 3f
l
(aS reactant1 3 10 on,ovgen 21%i
t/ A osPhe Oncent
Corlqolo% by yolume (pre-indusrial. in I 850) bo! in.reas n8 due to
aihropoSehic activity (was 0.017% bI lear 2000, now ncreasinS at a
proportona rute of -.0.4%/y).

Filue,A2 Pla.t level photosynrhesis.

10.2 Trophic level photosynthesis

Animals exist by obraining energy and marerials directly or indirecrly from
plants. This is called rhe trophic (feeding ) sysrem. t-i8ur 10.1 is an exrremety
simplified diagram to emphasise rhe essenrial processes of na tural ecology. We
should remember, however, thatthe box Iabelled .an ima ts' mighr ako inctude
the hurnan fossil fuel-based acriviris of indusrry, rranspo(! hearing,erc.

l0 2 Trophi. eve photo!yrthcs's 127

[oc os e

[lo t o ,t

H20
[ov o , t

C` b 1 ,jo

NADP

ttgure r0l Molcular level pho@syfthesis. Vedical scale indicates the x.iotion energ/
of rhe erecron. {a) Lisht reaction, indicannt rhe flow o, energl ahd matenak
in the Mo inleracdng photosysems ofgreen planB (b) Da.k .eacnon. ur,h8
rhe reducint atent produced from the liSht rea.tion oI pholosysrem I

Durrng phorosynthes,s CO, and H,O are absorbed to form carbohy.

drares, proteins and fars. The generalised symbol [CH]Ol ,s used ro indi.are
the basic t,uilding block for these producrs. CO, is relased during respi.
rarionof borh phnrs and arimals, and by rhe combustion of biolosjcal
materi.l This si'npl'fied explanarion is sarisfactory for energy studies, but
neglecrs rhe essertral roles of nitrogen, nurrie.rs and environnrenral param
erers in the proccsses.
128 The photosynrher. pro.ess
'I he ner trrcnly rbsorbed fro.r sol.t. r.drriion dDrins phoiostnrhcsis can
he nrersured fi ),n.ornbusrion. s'n..

,\H +COr + 2HrOa- lCH,Ol+ O, +HrO 1t 0.1)

.\H 460kl pr mole a = 4.8eV per arom C

= 16 MJ ks-'of dry carbohydrare materiat
Here AH rs rhe enrhalpy change of the combustion process, equal to the
energy absorberl from the photons of solar radiarion in photosynthesis,
Iess rhe energy of resp;rarion during growtlr and losses during precursor
re.crions. Al/ may be considered as rhe heat of cornbusrion. Nore rhar
combusrion requires temperatures of ''400'C, whereas resp'rarion proceeds
by catalyrrc enzyme reacrions at -20'C. The uptake of CO, by a piant leaf
rs a funcnon of many facrors, especially temperarure, COr con.e.uarion
and the intensity and wavelensrh d6rnburioDs of light (Figure l0.a).
Phorosynthesrs can occur by reducing CO1 in reacrions with compounds
other than warer. In seneral these reactions are of the form

COr + 2HrX - ICHrol+ xr + H.iO (10 1)

For example, X = S, .elating ro certa,n photosyntheric bacteria that grou

in the absence of orTgen by such mechanrsms, :s was rhe dominant process
on Eafth belore rhe presenr'oxygen"rich' atmosphere was fnmed.
The efficiency of photosynrhesrs a rs defined for a wide range of cucum-
siances. Ii x rhe raoo of the net enthalpy gain of the biomass per un,t area
(H/A) ro rhc ,nc,denr solar enersy per unu area (E/A), durins rhe parricular
biomass srowrh over some specified period:

(r 0.-5)

Here A may range trom the surlace area of the Earrh (includins deserts)
to rhe laDd arei of a forest, rhe area of a field of grain, and rhe exposed
or rotal surfacc area of a lea{. Periods ranse from several years Io m,nures,
and condiriors nray be narural or laborarory controlled. lt rs particularlv
imporranr w,'h crops ro derermine whether quoted growth refers to jusr rbt
srowins sean,r or a whole year. Table 10.1 sives values of rr for d,fferenr

The quanolles ,nvolved in a rrophic level descriprion of Photosynrh.sis

can be appre(iircd from rhc following example. Healrhy green leaves in
sunlight produce abour 3 litres o( O1 per hour per kg of leaf (wet basts)
This is an enersf flow of l6 w, and would be obrarned frorn an cxposed
 3
2
3

2 13tr7

_

13r

102 T,op `level Ph otOS nthesis 32'

r.t '/
r /00
-N

7 .(
/
3eao(C,p`ot)

///

2@ 4m 600
CO, .on.nmnorrppn
4_2
:

{-,a7v }v ,,r/
,..-tl\)W>

r``
r

2,`

/
/ /
7r
2
4 6 8
1nten,iO o ident 18ht
i

0 (a)C02 up ke offresh eaf a nc on ofC02con`ent on(b)[ (t
or extemJ ttctors on rate of Photosynthe [rect oF I t hten ,at 1r3 t
(A)25 C and 04%C02(3)15 C and 04%C02(C)2S C and 001% .==-.--
C02A un arO ra,Adapted from Hal and Rao(999)
/.\r r w
IcaF area oF abou[ lm= A persOn metabolizes at about 100 (res:ing),_
200 (aCtiVe ThuS each person Obtains melabOl c energy fOr 24 h From
rcaction with oxygen derived flom abOul 15-30m2oF leaF arca Thus in
CmPCratc reJOns one person pro ded annuJ b
t
lilm I:,

`uci cOnsumptlon rcqulre Far nlOre oxygen per person,c g abOul 100 trees
 ll0 Th. photosyntheric process

IoD,c /0/ Approxim:te photos/nthetjc efiicienq/for r ranSe oa.ircumst.nces Repoded

data vary wdelf for man/ dillerent circumstances

Ph otot nthet) c ef@ e ncy,

who, p/onr (ici photorynlher,

whole earth: I yea. averaSe tadhdoh incident benead rh 0l
ahosphere on to all land and sea)
Fo..n: annuil 6neal averate
Gasland,,nnual (vopi.al, avea8e: .empe6te well manated)
Cereal .rop close planled, tood farning, S.owi.g sason onl/
@mPeraie or rroPcal l
Continu.B crop: e.g cassava 2
liboratory .ondirions: enhan..d COr, Gmperature and
shlin8 oplmrsed. ample water and nuren6 5

lntnol photosynL\etk pro.ess (t.e not includnE plont rctpnotian)

Filterd ight, .onrolled condltons et. Th.orerical maxima: 16
primar/ Pholos/nthe.c exciton proce$ onl/
with tlre rea(tion ce.tres 20
w(h .:rbohvdr:re formaiion t0

per persoo the USA, about 60 in Europe, about 20 much of rhe

'n 'n
Morowitz {1969) argued that consideration of the bond energies rn pho-
rosynrhesis implies that rhe absorbed solar energy is predominantly srored
in rhe oxygen moleculcs and not rhc carbon compounds. The oxygen gas is
able ro move freely rhe amosphere, and eventually disperses rhis srore of
'n Earth's surface. In a siDilar manner carbon, in COr,
enersy evenly over tbe
rs also drspersed. The coupled reaction of oxygen with carbon compounds
has to occur before rhe energy can be released. Nevertheless, the usual
assumpion that food, biomass and fossil fuels contain rhe srored energy
rs acceprable as a basis for calcularion. However, appreciating thar plants
and rrees prcvide our energy and carbon-based mareri,ls rhroDgh easrly
drspersed gases rn rhe atmosphere provides an ins,g.ht inro the mechanrsms
of susrainablc cology and the need ro conserve trees.

10.3 Photosynthsis at the plant level

l0-3.1 Ab.orPtion of ltgh.
Solar .adiat(n rncidenr on a leaf x reflected, absorbed and rransmrmed.
far of rhe ahsorbed radiarion (< 5%) provides th nergy storcd in phoft)
synthesis rnd produces oxyBeDj rhe rema;nder rs absorbed.s sensible heJr
 l0l Phoro3ynrh313 a( the plant level lll

producing a rcmperature increase, or as larent heat for water evaporanon

(kinetic and porenrial energy changes arc negligible). Oxygen productton
is a funcrion of the wavelengrh of rhe rrdial'on and may be ploned as an
actrcn specbs'n, as inFisure 10.5{b).
Figure 10.5 shows typicalabsorprion and action spectra for a leaf Note
that photosynrhesis, as measured by oxygen production,

Abso P o

,05 Abrorption a.d adion spftta o, plant leaves and pEmenB (a) Iypi(al
spec.6l absorpdon spec@m ot a tren lear ,n ,vo (b) Adon rpe(rum
or atrpical sren plant dloll/di is the tpecral disribution ofthe rare or
orI$n produ.non perunitarea pe. unit radiation intensity (.) Absorption
spe(B of imporoN p'gmenB when sepaEted in laborarory .ondn'ont
h,(ro The grrphs 8ive the form oI the spech, whe.e absoQtion' r thc
propoEion of mono.hromanc aolar lradiance :bsorbed
ll2 The photosyntheti. prorss

04 05
W l 8tiV m

Fgt re' S(Con nued)

nearly rhe whole visible specrrm. Absorprion is usually mosr marked rn rhr
blue and red specrral regions; hence the green colour of most leaves. Spec
rroscopic technrques of great precision and variety are used to invesrigate
photosynrhesrs, but rwo basic experimenrs are fundamental:

The absorprion specrrum from rhe pigments of a living leaf is differenr

from the sum ofthe individual absorption spectra ofrhe same pigmenrs
separated by chemical merhods. Thus within rhe cooperative slrucrure
of an assembl), of pigments u airo, the absorption spectrum of.ny one
pigment molecule is changed because it is no longer isolared and rhere
are cooperarive inreracrions with other pigments.
For green planrs, photosynthesrs rocreases if there is absorprion tn one
pan of rlre spectrum, e.g. 700nm, and also simuhaneously at another
wavelenBth, e.g- 650om. Th6 is a furrher cooperarive effect, called rhc
F.nersoh effe.t, gNing slbsta ntia I evidence rhat phorosynrhesis rn green
pl,nr' rn rw,, thar rlr togerher rn
"..urr ',.rem\ 'are(.

lo-i.7 Sttu<tute of plon. leoves

A general snucture rnd scale of green leaves is given m ligurc 10.4, 1!
prrcrrce ihr(. rs exrensrvr varrety and complex;ry in allrhesc aspe.ts d(,wi
to nrolecuhr scale, as.lescrbed rn tcxts on plant ph],siobgy. In ourl,n(,

Phorosynrhesis occurs plart material, usually green leaves and algae,

'n h also occurs iD some srrnple organrsms
whrch we cors,der here.
(e s ptrrple hacr.n!) wirhour rhc assoc'ared Or produc,ng sysrem.
 t

Dll!12

038

5`o, o

0,3 ol , o tal
1 1,

Fg re /0d Structure and scale of plant leaves (e) Seclion o,a typicalieafol a broad'
l*led plant. Photos/ntnencally adve gren .ells are 5hown dotred with
chloropbtt orSanelles. Approrimate s.ale onl/. Actual celh p.e$ loSerher
more clo3ely lhan shown. i.e do nor h.ve Saps as big s indicated rn the 6gure
for dar,rr. (b) Sdion throuth chloroplast ortanelle. lhe lhylakoid inEmal
membnnes are shoq in the liquid slroma. Cetuin re8D.s have sb.ked
dylakod mcmbnnE Gne srana) which are (onne.led by unna.ked srom:
ramelhe membrane (c) Perspecttre of lhe tt2cked and unsBcked thylakoid
memb.a.e structure. SB.ked gEna linked by bridges olthe nroma lamellae,
all within the lquid sroma ot the chlo.oplai organelle. Approximate scale
onl/. (d) Thylakoid membhne shown tnctured by rreezins te.hniques along
natural lines of weakness. Four dsrin.t hes and surfa.es appea. outer,
PS (prolophsmic surli<e); innr ot outer, PF (proroplasmk h..); nner ot
innr. Er (ecloplsmic he): a6d o!!er of inner. ES (ectopl.sh'c turt.).
St2cked (subs.npB) and unna.k.d (u) resions a.e iden!6ed The inner
turhces show dis(inc! bumps with electron micros.op/ These bumps sem
to 6e asiocLaied with ATPand NADPH produ.tion Loose protein rtrucu.es
r$oci.led wilh CO: ass'mihdon are on the outer PS turiace Sructures
associarcd with O, and proton production are on the outer rnner surta.e
ES, (Note: ,n rro there it a sintle bilayer membrane, as rnd (ated n (e) )

1

(`1,

m

,S.
PF,
[F,
[S,
S kod m mb o Uo, kod b

ADP ATP
A` v , , o
V 0 0
" NADPNADPH

Cho,o,
T y`k `
/
P`Ot

mblo

4 /
[FPF

`
//

" 2! !!,
106 (cominued). (e) con.ep al diar!6 of rhllako d membrane oI the
wirh the liquid skoma beyond the ourer surfa.e. LH llghr
Srana sacks.
hanestn8 s/stem of pigment molecules about 5nm n len8th. Abour
20H00 mole,ule\ per r.a.non .enire RC rea.ton .enrr.s ipcn
merbrane ,boJt 20nm dEme(er !on
n'n8 rhe tlyrdLo,ds
moleclle completes ol abou! 50000 molecular weiShr. I and 2 indicate
the photosystems CF: .oupling lactor. Very larSe.omplexes produ.,ng
ATP and :llowin8 prorons to pump throo$ lhe membGne
 l0.l Photosy.thesis ar the planr level 315

2 The acr've cells of green pl.nts, e.g. p.lisade ,nd spong) mesophyll
cells of -0.J mm in length, have rnen:branes permeable ro sases and
water (Fisure 10.6(,)). These celh conrarn disrinct intracellular bodies,
organelles, aho having mentbranes.
3 The pho.osynrhrically active ell,pso,dal shaped organelles are called
chloroplasts. These are - 10pm long, and contain liquid, rhe siroma,
and membrane structure, rhe lamellaej see FigDre 10.6(b).
4 The lamellae have a layered structure that is io general errher stacked
or opn (unstacked) as shown in Fisure 10.5(c). The stacks are called
srana, and rh unstacked membranes are (roma lamellae. The open
srrucrure is linked to the stacks and naintains the enclosed pocke(s
withrn rhechloroplasr.
5 Thc lamellae are made of thylakords. These are like flanened balloons
having a double membrane srrucrure wnh four different surfaces (outer
top, inner rop, inner lower, outer lower) !s in Fisure 10.5(d). The
srmcture divides the chloroplast so the fluid may be differenr each
sid of rhe thylakoid lamella. This division is nor easily discerned in
two-dimnsional sections of chloroplasts-
6 The thylakoid membrane contains the components of the phorosyn'
theric lighr reacrion as in Figu.e 10.5(). These include the pigment
molecules, mostly chlorophyll, whrch absorb pbotons in a srructural
array like a telecommunication anrenna. This array is called the
antennd. The pigmenr molecules act cooperatively to channel rhe
absorbed energy'packet'(called an exciton) to cenrral reacrion cenrres.
The lighr rrapping and energy channelling sysren ts called rhe ligbt hat
,esti,a (LH) systm. There are about 30 pigment molecules associated
with each reaction centre.
7 Th reacrion centres conlain rhe final pigment molecules of rhe LH sys-
tems in chemical conlacrwith large molecular weigh t enzyme molecules.
Ar the reaction centre rhe energy from rhe LH system enables oxida'
tion/reduction reactions to occur in complex catalytic sequences.
8 There are rwo rypes of reaction cenrre in green plants rhat may partly,
bur nor enrirely, share LH sysrems. The cenrres are of photosystem I
and photosysrem 2 (PSl, PS2).
9 At PS2 racrion cnrres, protons and clectrons are separated from water
as Or ts produed, and some xcess nergy is used ro form energy
storage molecules AT? (adnosine rriphosphare).
10 Ar PSI readion centres, a strong reducing agenr NADPH (reduced
nicotin:mide adenine dinucleotide phosphare) is produced.
11 NADPH is able ro;n;riate reacrions to fix COr outside the rhylakoid
membrane in the outer liquid of the stroma. These reacrions can occDr
rn dark or light, since the productiott of NADPH has separared rhe
CO, uptakc from the immediare absorpoon of light. The reactions arc
called rhe Catm qtle dark reatttons
 116 The photos/ntheti. pro.ets

l' Ptorons, formed at oxygcn and ATI'p.oduction, are held by rhe rhy.
lakord membrane w'rhin rhe ioner res;ons ofthe lamell:e. During ATP
formanon the protons move down an elerrochemicalgradienr rhrough
rhe membrane ro mainrau the cycle of elements in rhe enr;e process.
1l In ihe Calvin cycle, COr from solution is fixed into carbohydrare srruc-
tures, and also p.otein and fat formation can be initiated.
t1 Photosynthetic bacteria zre prokaryo(ic ceUs (without inrernal nuclear
membranes) and the phorosynrhetically active pigmenrs are loared in
rhe membr?ne of rhe cell rtself. Only one photosystem, PS1, operates
and oxygen is not produced.

10.4 Thermodynami considerations

In this section we shall first consider photosynthesis as an asper of thermo
dynamics. The implicarions are important ro guide srr:tegy for renewable
energy researth and ro grvc hasrc underxanding.
Consider an ideal Carnot hear engine operated from solar energy (see
Section 6.9) ?nd producing work at efficiency 4 with a heat sink zt ambient
tenrperarure, say 27'C(300K). The heat supply is solar radiation. Wirh a
Ilat plate absorbing collector, rhe maxjmum source temperature is about
200'(1473K) and rhe maxrmum Carnor efficiency is 1473 30o)147t =
37%. l-or a power tower witb radration concentrarion on to rhe collecror.
rhe maxrrum Carnot efficiency .r'izht bc (773 300)1773 =51%. lt the
Sun's outer temperature could be used as the source, the maximum Carnor
effrcrency would be (5900 - 300)/5900 = 95"/.. Thus from an eng,nering
pornt of view, there is much intersr in seeking to link processes to the
largest temperature available to us, namely rhe Sun's remperarur.
The only connection berween the E:rth and the Sun is via solar radraoon,
so a radiarion absorbing process is needed. If the absorption is on a black
collector, the process is temperature limited by the melting poinr of the col
lector material. However, ir is possibl to absorb rhe radiarion by a photon
process into the electron states of a marerial wuhout immediarely increasing
the bulk temperature. Such a process occurs in phorovolraic power genera-
oon (see Chaprer 7). Ler us compar rh two prcsses, nanly rhermaland
phoron excrtation. FgDre 10.7 represenrs a marerial that can
elecrronic states, normal and excited. The difference between rhese srares
is solely the different elecrronic configurat;on; the core or'lanrce'ol the
materral remains unaffected.
ln F'sure 10.7(a) rhe exc,red srare can only be reached by hraong the
whole material, and the proponron of excited states N" ro normal states N.
rs crlcularcd as for rntrrnsic semiconductors:

N"/N, : exp( (r0.6)

^a/I7)
 101 Therfrodynami.conrrderationr 137

Condu.r'on .\.trcd n?re (b) Conducrron excn.d nar.

`>kr

Nom.l tl.t.
f,gure ,o/ Eldrd ex<iE on by (a) heat and (b) Photo aborPtjon. The veEol !.ale
indi<ates d'e ex.iEtion 4er&, of the dron

We shall be considering pigmenr molecules where aE-2eV, and T<

173 K = 100'C, since the cellular matenal is water based. Thus N"/N" -.
10-17. Even ai the Surt's remperatur of 5900K, N./N. = 0.02. k is con-
cluded that thermal cxciratron does not produce many exciled states!
However, m Fisure 10.7(b) the excrled lct.onic stare is formed by
electromagneric absorprion o{ a photon of energy Du 2 AE. This process
does not immediarely add energy ro the remaining 'larrice, which remains
ar the same temperrrure. The popularion of the excned srate depends on
the rare oI absorption of phorons and coupltng of the excrted elecrronrc
stares io the 'larrice'. Ideally, rhe population limir rs N. = N", when the
radiation is transform'ns equal numbers ol srates back and forrh and the
electronic reftperatur rs effecri,ely ,nfinire. Ths ideal is nor reached in
practice, bur th rheory of the preess explaios how 1010 more elecronic
excited srates can be formed by electronic srate phoron absorprion, rhan by
rhermal exciration.
Th rhermodynamic analysis rs nol complete unol the energy has Per-
formed a funcrion. In photosy.rhes,s rhe solar energy is rransformed into
excired srates by phoron absorPnon, and the energy is eventually stored in
chemicat producrs. There is no produdion of'work' in rhe normal mechan-
ical ensineering sense, but work has been donc rn the producrion of orsani
material srrucrures and of chemical srores of energy.
The chemical changes occurflog in photosynthesis are in some ways
similar ro energy srare changes in semiconductor physrcs ln chemistry
rhe changes occur by reduction and oxidanon. The ledu.tion leuel lRl is
the number of oxygen molecules per carbon atom needed ro transform rhe
material ro CO, and H1O, For carbon conpounds of the general form
qH/,O,,, the reducrion level ,s

R: . +o.25h 0.so (10.7)

Th nersy to form rhese compounds from Col and HrO pr unir reducrion
levcl R ,s about 450 kJ per mole carbon.
 ll8 The photosyntheti. pro.ess

I
I
I
I
I
I
I

I ICH,ol C..bohydr.l.

rl
rl
rl
I
I I
I
t

Subt ction
of d t 0

Fordet,w
F,t"#
FEUe ,O8 RedGion revel R of orbon comp@nds. EndDtpI chlnte pr arbon
.rom, AH. of ch.mic.l <@plei .ebrild !o COrlHrO.

The relationshrp of rcducion level ro rhc .nergy srrtcs involved in pho-

tosynthesis is shown io Figure 10.8. Photosynthesis is csscnrially rhe rcduc,
tion of COr in rhe presencc of HrO ro carbohydrate and oxygen. In rh
process four elecrrons have ro be.ernov.d from four molccules of water,
Figure 10.9. The full process will b. cxplaind in Section 10.6.

4H,O g 2H,O+O: +4H* +4e-

10.5 Photophysics
Th physical aspecrs of phorosynthcsis involve the absorption of photons
of Lghr by elctrons wirhin pigmnr molecules. These molecutes absorb rhe
nergy ro form excired starcs. lghen the molccules are isolard, rhe ene.gy
is usually re'emrrted as fluorescenr radiarion and hear. However, whn ihe
pigmnrs are bound in chloroplast srrucrures, the maiorhy of the energy rs
transferred cooperatively ro reacrion cnrres for chcmical reducrions, wirh
th excess comins our as heat, and rhere is li$le fluorescence.
The rsolaied properries are xplained by rhe Franck-Condon dragram
(Figu.e 10.10). This porrrays rhe ground and cxcired enersy states of $e

n\
Foo, Ct,0 ,, OVOd

,ts\ b*
,z--\
(.'o'.1* {:o:)
\6./ \.6r./
U{.'
Hro

n,o
-\o,
,,o *\ or-

figrE /O9 Redudd of Eter to oxy8.n and protons at r@ctio. cenoe of P52 -
four el<trons are removdl

aHro g 2Hro + o, +4H+ +4

Sprrirl c@rdinar.r- l0_ro(

figre ,OI0 FGftk-Cdd@ diagnm illu*nEngSrok6 sh{t in eoery beMeen d'e

absorbed phoron A and dre fluor6rsr phord F Th spatial ce
o.dinlte r indicates ihe ch.n8e in posilion or size betwen ihe ex.ited
tystem and I ground sbre.
 140 The phoror/n!he!ic pro.est

molecule as, fun.iion of the relaove pos,rion of 'rs aiohs. This rel,rive
posnion is measured hy some sparial coo.dinare, su.h as rhe disrance r
ber.aeen two parrcular neishbourins atoms. Note that rhe mrnima in energy
occur at different values ofr owing to molecular changes in size or posirion
after excitarion. A photon in radiation, travellng ar I x 103ms I, passes
the molecule ofdimenson'10'm in rrme .'10 rrs. During this time
elcrromagneric rnreraction wirh the electronic state can occur, and the pho
ron enersy of - 2eV 6 absorbed (A). However, vibrarional and rotational
morions are occu.ring ri lhe molecule, with the.msl energy tT - 0.03eV
and period--10 rrs. Ihese srates are indicated by horizontal lines on the
dugrum a, thc molc,ule oqcrllares about rts mrnrmum enF'gv po(,ron\.
Absorption (A) takes place too fast for the molecule structure to adiust,
and so the excrred srare is formed away from the minimum. If the excrted
electron r paired w,rh anorher elecrron (as will be probable), the excned
srate will be expected to be a singlet state Gpin =1 .l :0) wirh liferime
l0 3r.
During rhis rime of 10 3 s, rhere are .' 10J molecular vibrations and so the
excited srare relaxes ro the minimurn of excited energy by thermal exchange
ro the surroundings. Afrer rhis, one of rhe following rwo main processes
occurs w'th the release or transfer of rhe remainins exciradon enersy.

The molecule is close ro othcr similar molecules, and the absorbed

energy (called an excrron) rs passed to rhese by .esonant transfer linked
.3
w,rh rhe rhermal morion during the l0 s lifetime. This is the dominant
process for prgment mole.lles in uiuo.
Afrer .-10 3s, fluorescent cmission (F) may occur as the molecule
returns ro rhe ground srare. The wavelength of fluorescence k longer
than rhe absorbed lighr, as described by the Stokes sbift. Aherna
tively the electron may changc orienrar'on in rhe excired state, by
magnetic inreracrio. with the nucleus, to form a ripler srare (spin:
++
.l= 1). The lifenne of rripler srares is long (- 10 r s) and again loss
of energy occurs, by phosphorescence (P: Figure 10.11i or by resonant

Resonant ttansfer canoccur between molecules when they areclose (.'5 x

10 r0m), and when rhe fluorescence r:diation of the rransferrins molecule
overlaps wrh the absorptron band of the nerghbour (Figure 10.12). In lhese
condnions, lhe excned eleclrcnic stare enersy (rhe excrron) may transfer
withourradiarion ro rh. Dexr molecule. Separate energy level diagramsofrhe
form of F,sure 10.11(a) may describe this or, when molecules are very close,
by a graded band gap dragranr like liisure 10.13(b). In e,rher des.ription
rhere sparial rrander of energy down a potentialgrudienr through the
's: of molecules. The process sim,lar ro coDduction band elecrron
asembly
's
movemenr rn greded gap photrwoltaic cells; see Sect,on 7.7.2(5). Howcver,

2, lt

O S' Li

/ =

G oo d,t,t


0 1
S,at 1 oo,di 10 m

ro,r Triplet
tbte d phosphorercen! photo. P. Hweve.. dte ex(ited
and troundses ma/ overl.p, so reom to ground sore ma, @cur
wirhom emiaed radiation.

t

(o-'r gn;(1, >t*uJ

___

Ovcrlap ol A nuoEr.n..
*nh B ab$rprion to siv.
pGrbility ror ..snanr lrmsr.r
of...Ay ofhol.cu!.s in c6nra.r

FSUrc /012 Resonant ransfer o1ner8/. Theabs.irsa is rhe wavelength ofthefu-

ores<nce a.d absorption bands ot sepa.ard molecules. The ordinate
indic.(es the intens ry ot the bands.
142 The phorosyn!he!i. pro.ess

Re, oo o tO

Fauft loll fransl.r ol enero,b, P't@nt mr(d$ of rhe LH tFtem to the

p.rccuhr rea(lo <entrc. (a) SpEdalPoeoon of LH Prgmst molecules
(m, n, o. P) tnndernnt dere/ b. re.<trd c.nre R. (b) Gaded b.nd
tap model: .ontinuo6 elet.@ic artucture of LH PiSment rclEculet
..D.t as a continuout 3uPer mole<ule.

in photosynthesis, enerSy is rrans(erred as whole molecules slighrlv adiust

their position and srructure durinE elcctronic excirarion and rlaxation, and
nor jusr by rhe rransport ol a free electron-
There rs nevertheless a mosl significanr difference between electron
(ransporr in photovohaic semiconducrors and energv transport in pigmeni
moleiules. rn photovolraics the srructural marerial is manufac(ured with
graduated dopanr properties across rhe cell. Each lement of marerial has a
precise dopanr level and musr remain aI the suirable locarion. If the phoro-
vokaic cell rs broken up, each prece kePs rls distinguishing characteristi'
However, in (he phorosyntheric LH system, ri is th.oope/a,iu? stractrre
of all rhe pigmenrs lhat gives each pigment lhe necessarv electronic struc
rur. required fo' its prectse location. k does not matter where a pigment
molecule finds iaelf; ir will always be given the correct proprries to fit
rnro rhe l.H array, suirahte {or its posrtron. So when the'arrav'rs broken
up, each prgnent isolared properries Thrs :ccounts for rhe
difference between in u ,a and i riho proPerries of pigment molecules'
duri s rbsnprron and fltrorescence.
 lO 6 l'1ol.ular levei phoros/nrhes's l4l
10.5 Molecular level photosynthesis
The previous sectlons have outlned the whole photosyniheric process. ln
rhrs secrion we shallcons'dersome ofrhe phys;ca I dera ils, although we sFess
that rnany of ihese are not fully undercrood and are the sub)ecr of acrive
research. Note rhar we purposely do nor include biologrcal and chemical
derails, srnce rhese may derracr from physical undeBrandrns and also such
derail s well descr'bed elsewhere, e.g. Vrigglesworth, 1997-

10.5.1 Light horuesting and the reactton centre

The photosynrhetically ative ligh s absorbed in prgment 'lanrenna'
molecules, of which the mosr common is chlorophyll rype (a). Orher
pigDenrs occur of similar rnolecular srructur and shape. A chlorophyll
nolecule consisrs of a hydrophobic (warer fearins) tail and hydrophilic
(water lovins) rins. The rail is a lons chain hydrocarbon (phnyl residue
CroHe), about four times longer rhan rhe'diameter'of rhe ring. Ir seems
rharnosr of rhe anrenna chlorophyll molecu les are embedded in chlorophyll
pigment proteins, which in turn are embdded in rhe rhylakoid membrane.
The tail is presumed to be fixed in rhe thylakoid membrane's outer surface,
wrrh the ring in the water-based srroma of the chloroplasr (Fisure 10.6(e)).
Light phorons may be absorbed by the molecules, wbich are close enough
to (l), cooperarively intera.r ro produce wideband ir uiuo absorprion, and
(2), ro channel (harvest) exclted srare ene.sy excirons down a potenrial
sradient by .esonant transfer ro rhe reacr'on cenrre. Asscmblies of abour
200-400 piBnenr molecules occur as cores', each containrng one rerftion
centre. Assemblies with less or more pigmenr molecules per reacrion centre
occur in some specres of plant, algae or photosynrheric bacteria. In general,
systems adapred to weak lighr have rnor pigment molecules per core.
Photons may be absorbed at the outer or inner LH molecules, and rhe
resulring energy excrron passes to.he reaction centre alons paths of least
resistance. This consisis of rhe final pigment molecule and some very large
specialised molecules (molecular weishr -50000) in whrch rhe'chemistrl'
occurs. Most evidence for rhis general srructure of parallel Lll paths to a
central centre has come from optical absorprion, fluorescence ard acrion
spectra Iinked with light flashes ofvarying intervaland intensny. Two types
o{ core exrsr, one for each of phorosystems 1 and 2. It is possible for
different cores to share rhe same LH arrays.

10-6-2 The light reo<tions

The physical processes of phorosysrems I aod 2 (PSl and PS2) are sim,lar
(I'isure 10.14). The lisht harvesrins (LH) system channels exenons from rhe
inirial quanra ro rhe reaction cenrre, where dre lasr mol.cule ot chlorophyU
 114 The photosyntheti. pro.ess

A,

r photon,Ps
A2 (l

NADP NADPH

oi-D,

+ojo,
/ \, lHro

tt
I LshrF,oon lo"a ..,.""n
III *in- -"-b,-. 1",",a. -.-r-..-
l- Psr r6so) ___.1_ Psr poo) _J
FiluE ,A14 Th. Z tcheme of pho(osntheris,t dre reaaioi.enEei eidr photos
per C fixed The venicar <.le indicates lhe erciErion e;i, oa the
el4tron.

in rhe sysrem ;s used to identify the particular centre. This is called P680 for
PS2, and P700 for PS1, since the respecrive molecules absorb distinctively
at 680 a 10nm (1.82 eV) and 700+ 10nm (1.77 eV) respectively. Nore rhar
borh rhese molecules absorb at the red end of the spectrum ind;cating their
position at rhe lower porential energy end oF rhe LH sysrem.
In the reaction centre there are both donor and acceptor molecules. (These
names are used in ihe sens. ofsemiconducror physics. However, beware rhar
rhe lefter p may be used for pisment donor molecules, in rhe oppor,te sense
of p'rype semiconductos.) The channelled excnon trom each absorbed
phoron lifts an electron from the particular donor (D)to the acceptor (A).
Chenical reacrions rhen occur with rhe D+ and A radicals so formed.
These reactions are cyclic, so D and A are reformed by rhe transfer of
anorher.lecrron ro D. and rhe exored elccrron from A. Two sers ofchemical
re.crions occur, one set as l)' rerurns to D, a d rhe orher ser as A rerurns
ro A. These chemical reanions ,re complex and nor yer fully derernined for
rhe many variarions of detarl that occur. However, rhe physical processcs
rre clear. Nore especrally how rhe complere proccss utilises mulnple photon
 106 Mor..u ar lev.lphotosynthesis 145

absorprioo and electron excitation sreps pcr molecule o{ Or released and

Co, absorbed.
For green plants there are five d,srincl sreps of rhe Z scheme as illustrared
rn Figure 10.14 and also Fisure to.l: gj AdA
E
I Di - Dr. -Dj is formed by electron exciranoo of PS2.rk r a srrons
oxidanr (attracting elect.ons ) with a redox potential of +0.9v. There is
evidence rhar Dl is a chlorophyll {a) molecule, or molecul,r pair, in rhe
non aqueous environmenr of rhe rhylakoid memb.ane. Th oxidisins
ation of Di is ro exrraci an elecrron from HrO; wirh rhe uhimate
resuh thar one molecule of O2 is formed by four Di reacrions, see
Secrion 10.4 and Figure 10.9. The O, molecules diffuse through the
various membranes and out of the plant cells. The protons, H+, remain
in the thylakoid mmbrane double layer.
A ) Ptotan abtotDtion in PS2. The donor D relea'e, an ele.tron thrt n
" t'6.a ,o acceptor Aj. lorm,ng A:. A, ha. be.n grven rhe lab.l Q b)
research workers and may be a plasroquinone. (Nore that M'tchell's
'Q-cycle' is involved in rhe movement of protons from PS1 ro PS2.) A,
is a mild teducranr of redox potenoal abour -0.1V, i.e. the potential
energy stored by phoron exc'ration when ?n elcrron rs rransfered from
A. to D. changes from 1.0 to l.l eV. Dr at sgrq!j!q80 + 10nm.
1 LinA betueen PS2 a"d PSt: ATP ptudu.tion. Afrr A; formarion,
a series of reactions occur ro rrander the elecnon down an energy
potetrrial ro Di ar redox po.eniial +0.4v. The energy difference is
used to form the energy storage molecule ATP (adenosine rriphosphate)
from ADP {adenosine diphosphate) ar 0.34ev per molecule. Minimum
AT? producrion seems to be rhree ATP per four operations of PS2 and
PS1, as required for the Calvin cycle (Secrion 10.5.3):

ADP+P, + ATP + HrO i10.8)

where P, denores inorganic phosphaie.

4\a lhoton abso,puo, i, Ps,. lurrher phoron rb\orp,,on ,hrousl, ,he LH
ry\rem ro rhe ,eacrion cenrre of Psl !e\ulr' rn rhe formJtion ot Dj
and Ai. Dr appars ro be a funher chlorophyll (a) monomer or pair
(absorbing ar 700 + 10 nm ). A I rs a ferredoxin protein.
5 NADPH Ptodqction The elecrron raisd in energy porenrial ro Ar then
passes to form NADPH from NADP'. NADP stands for nicoon.mide
adenrne drnucleorrdc phoqphrre. lb redu.ed rorm s NADPH,,nd I.
oiid;sed form is NADP*, somerin:es conlusingly wrinen NADP.

NADP++2e'+H*-NADPTI (r0.9)

Thus each reducrion of NADP* rcquires two electrons, from two oper'
146 The phoro3ynthei. pro.ess

10.6-3 Do.k.eo..ionr (Cottin.y<t.)

The formation of NADI'H by PSI supphes rhc marn reducrng agent required
to fix CO, inro carbohydrare. Subsequent rcaenons occur by ordinary ther-
mal'chemistry, not photochemisrry, and so may occur in rlre dark a/rer a
period o( lieht absorption, as well as dwng perrods of lighr absorption.
The reactions -rhe Calvin cycle occur in rhe srroma ourside rhe rhylakoid
srructures, but within the chloroplast. The re.ctions nay he followed using
rhe.adioisotope raC- In phorosynrheric brcleria, PS1 is rhe only phorosys-
rem, and Cor frxarion occurs with no O, producrion (since rhere B no
PS2). hr sreen planrs, chemrcal products from rll tluee sers of reacrions
associated with PS2 and PSl (Di, A; and Oi)are used in rhe dark reac
rrcn. Thus the main in;tial inpurs for the Calvin cycle are NADPH, ATP
and Il+ from the phorosysrems, and CO, and H.O from the environment.
A complex of intermediar chemicals and numerous c.ralyric enzymes is
required within rhe cycle (e.g. the enzyme Rubis.o, r.e. rbulose biphosphare
carboxylaseoxygenase). Tbe prorons are made available from within the
thylakoid membrane by the varjous 'pumpins' mechansms. In the chemical
equarions below, P indicates inorga.ic phosphare.
Assimilarion of COr is described by:

3COr +9ATP+ 5NADPH + 5H+

- CrH'OrP + 9ADP + 8P, + 5NADP* +3HlO+e (10.10)

while the overall Calvin cycle reaction can be summarised as

cor + 2NADPH +3ATP+2Ht

+ [CH]Ol + 2NADP+ + 3ADP+ 3P, + HrO (10.11)

Thus rwo NADPH are required per C (rxed from reduced CO.. Each
NADPH requires two electrons from rwo operations of PSl ro be reduced
again to NADP, cf. (10.9). Thus the Calvin cycle rs powend by four photon
absorptio.s in PS1.
The firsr product of the Calvin cycle rs a three carbon (C1) compound
rn most planis, as in (10.10). Certain rropical plants (e.s. susarcane, maize
and sorslun) have a preliminary chemical cycle involvins a Ca compound
bcfore rhe Calvin cycle. These Ca planls hirve rwo differ..t rypes of pho
tosynthetic cells rhat function cooprarivtly rn rhe plant. In moderare ro
srrong lighr inrnsiry (-0.5 k!v m r) and elvared remperatures in the leaves
(''40"C), rhe C fixarion and hence biomas producnon of C, planrs may
b rwice rhar of Cr plants.
 106 Molecular level phoros/"thesis 147

10.d4 Nlnber of pho.ons per <orbon fixed

The main requiremenr tor light absorpnon 6 rh,r photons can
'ndividuat
be absorbed, and the energy stored for sufficienr rnne ro be used rn larer
chemical reacrions or further phoron excitarion. Thus each photosysrem is
triggered by single phorons. If rhe molecules oaone sysrem a.e ,n operarion
and so taturated', rhen ir seems rhar rhe excnon can be passed ro orhers.
A minimum of four operarions of PS2 are needed ro produce one motecule
of O,, i.e. four lecrrons have ro be lifted off H,O, see F,sure 10.9. Four
orher photons are ncdcd ro produc rhe NADPH for CO, reduction. So in
green planrs w'rh coupled PS2 and P\|. at lcan etght phot.ns are needed
to fia one C aton as carbohydrare. In practice ir seems rhar more photons
are needed, either because an effecrive chemical saruraoon or toss occurs.
or because further ATP is required. Thus most planrs probably operare at
about ten phorons pcr C fixed in optimum condrtions.

10.5.5 Energy..ot.s
In the simplified reacrion (10.1), rhe encrsy difference of C in lCH,Ol :nd
CO, is 4.8eV. This averages 1.2eV each cycle, per four cyctes of pS2 and
PS1 together. The l.2eV may be accounted for ar rhe racrjon cenrres bv

-0 2eV O: formation by Dl
1 leV absorprioD by PS2
-0 5eV link of PS2 and PSl, ATP formarion
+1 0eV absorption by PSl i
-0 2eV NADPH formarion

The signs of these energies are used in rhc sense of ele.tron excirarion of
physics. The chmical redox potentials have opposir srgn, buthe essenriat
meaning is the same. The zero energy is wirh separared CO, and H,O
before solutions are formed and rhe reacrions begin.

10.6.6 Efti.ienct of pl'otosynrherk

This may be defined in vanous ways. The minimum phoron enersy inpur
ar the outside antenna pigmenr molecules (i-e. ,or ar rhe reaction cenrr)
may be given as four phorons of 1.77eV (PS2 absorpoon for D, ar 700 nm)
and four of 1,82-eV (PSl absorprion for D, ar 680nn1), roraltins l4.4eV.
The rLruJl exc,'.rons D. io A,. and D, ro A,. a,c abour r.teV i,.tr. so
four operarions of cach require 8.8 eV. The ourpurs may be considered ro
be four electrons lifted from HrO ro NADP over.edox pore.nal t.tieV
(4.50 eV) plus rhree AT molecules ai 0.34 eV each (1.02 eV) ro e;ve a roral
 148 The photosynthetjc process

output of 5.5 cV. The ourpur may .lso be codsidered .s one O, inolecule,
and ofle (l ,rrom fixed in carbohydrare, requirins 4.8 eV.
A reasonable maximum efficiency from light absorprior ro final product
can be raken as 4.8/14.4: l3%. The l,rger proporrions of 5.6/t4.4,5.6/8.8
and 4.8/8.8 may somerimes be considered.
In discussing phoron inreractions, rhe unir of rhe ?,"5r?,, is ofren used.
One einsrein is Avogadro's number of photons of rhe same frequency, i.e.
one mole of identical or similar phorons.
Thc solar specrrum consisB of many phorons wirh quanrised energy
roo small to be photosynthetically acrive (i > 700nm,r, < l.8eV), and
phorons of grearer energy rhan rhe mi.'mum necessary {}r > l.8eV). The
siruarion very similar to rhar wrrh phorovoltaic cells (see Figure 7.i2
and Seclon 's 7.4),
so that only about 50% of the energy of rhe photons
phorosyntheiically absorbed is used ro oprate PS2 and PSl. Ths effcr
would reduce the maximum efficiency ro about l5%. However, leaves are
nor black and there is cons,derable retlecrio. and rransmrssion, reducins
the maximum efficiency to-algqr 12%, considering only (he solar radiarion
incident at rh phorosystms. Efficiencies near ro rhis hrve been obtained
in controued laborarory conditioos. Consideri.g solar irradiarion on land
sene.ally, whjch will include parts other than leaves, such larse efficien-
cies are not reached in even the besr agriculture, or in narural condidons
lTable 10.1).

10.7 Applied photosynthesis

Tchnolosy conrinually advances from fundamenral srudies in sc;ence. The
same process will follow th evenru.l (ull understanding ol photosynthe
sis in its many varied details. Thjs section considers some energy,relared
applications, both currenr and potential.

l0.l.l Plont physiology ond bto,,-oss

Plants are being selected and bred io be berrer suired io rhen envnonmenr.
Examples have already resuked from undenranding why C, plants are more
producrive in srroager light intensny rhan C, planrs, see Secrion 10.6. As
biomass energy becomes more irnportanr (see (lhaprer I I ), plants are being
selecred and developed ro opt;mise fuelsupplies.arher rhan jusi rherr arurt,
grain or similar parl producr. For insrance, propagation from clones of best
Plants and applicarion ofgenetic ensrneering have increased phorosynrheric
efficiency for b'omass producrion. Cons'deBble research concerns the func-
rionin8 of rhe RDbisco enzyme, wirh a vrew ro evenrually designing' a form
of Rub,sco wh,ch aUows increased carboxylarior ar rhe expense of rhe side
reacnons which now occur narurally, notably oxygenarion. lr rs con.erv
able rhat arrificial carbon based slrucftres, marerials and food could be
manufacrDred from syntherically conrrolled forms of phorosynrheys.

10.7.2 Hydrogen P.od!<tion

The free protons formed during rhe operation of rhe photosynrheric cycles
may, in some insra.ces, be emined as hydrogen gas. The H+ ions are reduced
(have an electron added) from rhe accepror Ai of PSl. This reacrion 6 aided
by certain natural enzyms (hydrosenases) and does occur narurally, e.g.
w,rh rh. bacreria bactetiothodopsin and ,n human merabolism associated
wirh digestion defiiencies. ln general, howev., hydroaenases are inopera-
rive in the prsnc of Or and, if Hr is em'(ed, the concenrrarion extremely
small. Nevertheless, the prospecr of producing considerable 's amounts of
hydrogen from chemical ractions activated by sunlight is potentially very
important commercially and warrants continuing research.

l0-f-3 Phorochemicol ele.rtl.l.y produ.tion

The driving function of photosynrhesis rs the phoron'inducd molecular
excitations of PS2 and PS1. These involve electronic excitations wrihin
molecular s.rucrure and charge separanons, and are nor exacrly .ompara-
ble wrrh elecrron-hole separation across rhe band gap phorovoka,c devices.
Nevertheless rhese molecular excitons have sufficient energy ro dnve an
externalelectric circuit, and research and development continues for phoro
chemicalpower devices. A number ofrelatcd devices are avarlable, includins
the dye+ensrrive celJ (Figure 7.23). The advanrage over convenrional pho-
tovoltaics might be rhe manufacrure of the base marerial by liquid chemical
merhods in bulk and th manufactur of s'nrle dvices rhar borh srore elec-
rriciry in sunliBht and provid electricity as a battery. Such developments
trom photochemrstry may lrd ro rrd,!al innova,,on.

Problems
10.1 Calculare very approximately how many trees are needed (r) to pro'
duce rlre oxyse, used for your own met:bolism, and (ii) to mairtain
rhe per capira rotal fuel consumpoon of your counrry. Compare thrs
wrrh the approxrmare number of rrce. pcr pe,\on i. your counrr)
10.2 The heat of combustion oi sucrose C,,HrO,, is J645k.lmol '. Cal
culare using the Avogadro consranr, rhe energy pr aronr of carbon nr
150 The photosyn!hetic pro(esl

Bibliography
U n d c.Cro d ! a.e -l e y e I b ooks
Hall, D.o. a.d Rao, K.K- (1999) Phorosynthe,s l6th edn) Edward Arnold, London.
lA shod and *imularins introducrion wtrh hore physical bias (han n,any orh6.1
Lawlor, D.w- (2001, lrd ednl Photosynthesn: Moleculat, Physoloql@l dhd Ekui.
/ohne tal Proceses,RIoS Scieorific P!bljcarions, Oxfo.d. (Con.isdcxt Ior biol
osy undergraduares.)
Montcth,J- and Uoworrh,K.11990,2nd edn) Pinciples of Enuircnnentol Phyi.s,
Edward Arnold, London. {Consid.6 fi. physical hreraclion of planr and animal
lif wi(h ihe environneni. Chemi.al asp.cts are.oi considered. of background
rcl.va.ce io phorosynrhesis.)
Morowrtr, H.J. (1959) E,ery, Floo i" Blology: Biologt@l OrSdn&tto, as a kob-
len n Thenal Phyi6, A.ademic Press, New York. 1A stimul,rin8 b6l with
lateral thinkins for corside.itrE phys,c.l processes and coflsrraints.l
Writtieswonh,J.(1997)Ene/sy dnd Li{e,"tayl6t UFranc6, UK. lThebi@hcDistry
of m.raboljsm and photosynthesis, .l.erly p.esenred.)

lournols and w.bsites

Phoiosyothens is an erremly a.tiv. area of scientific research, with mosr of that
r.search (>1000 pape6 pr y.ar) rcpon.d iD spialist sientifi. tourtuls ruch as
PhotosrnthesB R.scarch, Annel R.oitu ol Plokt Pbrsiol , dnd Pldhl Mole.uldt
Bloloty, Natute and Photo.benistry and Pbotobiology. Much of rhis work is rhen
disrill.d'nro Bmduarelevel monogaphs.