Termodinamika Reaksi Biokimia: Tik: Mahasiswa Mampu Mengaplikasikan Konsep Energi Bebas Dan Redoks Dalam Reaksi Biokimia

Termodinamika Reaksi
Biokimia
TIK :
Mahasiswa mampu mengaplikasikan
konsep energi bebas dan redoks dalam
reaksi biokimia
Termodinamika Reaksi Biokimia; ITP 240
Pokok Bahasan
Pengertian Dasar
Hukum-hukum Termodinamika
Energi Bebas
Redoks
Contoh-contoh soal
Tetapan yang sering dipakai
Energy & Metabolism
All living things require energy

One of the primary functions of
macromolecules is to provide
Energy
Energy is the ability to do Work
Energy exists in two forms:
Kinetic Energy
Potential Energy
Energi Potensial dan Kinetik
Bentuk : Mechanical, Sound, Electricity, Light,

Radiation, Heat
Heat
Useful way to study energy because all

other E. forms can be converted to
heat
Heat Energy measured in units of
calories or kilocalories
This is the study of Thermodynamics
Thermodynamics is a branch of
physics which deals with the energy
and work of a system
Energy Flow
Ultimately, all E. for life on

earth comes from the sun
Sunlight shines 40 million
billion calories/second on
earth!
Plants, algae and
photosynthetic bacteria
convert sun E. to sugars
Photosynthesis converts a
small (~10%) amount of
sun E. into covalent bonds
Where does the rest
(~90%) of sunlight E. go?
Energy from Chemical Bonds
Chemicals may be considered from a potential

energy or kinetic energy standpoint.
One pound of sugar has a certain potential energy.
If that pound of sugar is burned the energy is
released all at once. The energy released is kinetic
energy (heat).
So much energy is released that organisms would
burn up if all the energy was released at once.
Organisms must release the energy a little bit at a
time.
Example of the Energy in Covalent Bonds
Photosynthesis:
6CO2 + 12H2O + Light E. C6H12O6 +6O2 + 6H2O
Light Energy requirements = ~3,000-7,000 Kcal
Respiration:
C6H12O6 + 6O2 6CO2 + 6H2O + Energy
Energy released = 686 Kcal
Energy Loss in each Energy Transfer

Photosynthesis uses lots of energy
(3000-7000 Kcal) to produce one
glucose molecule
But, the energy released from one
glucose molecule produces only 686Kcal
Most of the excess energy is lost as
Heat.
..but the energy is never really gone
The Laws of Thermodynamics

First Law Energy can never be created nor
destroyed.
The total amount of Energy in the universe remains
always the same, it just changes forms
Energy can be exchangedbetween systems and
their surroundings However, the total energy of
the system plus the surroundings is constant.
That's the First Law of Thermodynamics.
The First Law is also stated as energy is conserved.
How do we know this?

Thisisanempiricallaw,whichmeansthatweknowthatenergyisconserved
becauseofmanyrepeatedexperimentsbyscientists.It'sbeenobservedthatyou
can'tgetanymoreenergyoutofasystemthanyouputintoit.
JamesPrescottJouledidafamousexperimentwhichdemonstratedtheconservation
ofenergyandshowedthatheatandworkwerebothofthesamenature:energy.
Hisexperimentinvolvedwaterinathermallyinsulatedcontainerandapaddle
whichwasconnectedtotheoutsideworld(surroundings).Joulefoundthatthe
amountofenergycouldchangefromoneformtoanother(worktoheat);
however,nonetchangeofenergyinthesystemplusthesurroundingsoccurred
andthusEnergyisconserved.
http://www.secondlaw.com/two.html
The First Law of Thermodynamics
The first law is very simple: You can't create or

destroy energy.
You can just change it from one form to another, e.g
electricity to heat,
heat that will boil water and make steam,
hot steam to push a piston (mechanical energy) or
turn a turbine that makes electricity which can be changed
to light (in a light bulb) or,
using only a tiny quantity changed to sound in an audio
speaker system, and so forth.
The Second Law
Energy spontaneously tends to flow only from

being concentrated in one place to becoming
diffused or dispersed and spread out.
A blowout in a tire and lightning -- what
could seem to be more unlike than those! Yet
the reason for their occurring is the same,
the tendency for concentrated energy not to
stay localized, to disperse if it has a chance
and isn't hindered somehow.
The Second Law
Energy is constantly being converted

to random molecular motion (heat
Energy)
This random motion is less ordered
(disordered) and is always increasing
The universe is becoming more
disordered all the time
Disorder = Entropy
And Entropy is always increasing
And so
The Universe is Breaking Down
Entropy is increasing
It takes constant E. inputs to keep a road in
good shape, your car running and your dorm
room clean
Leave things alone and things fall apart
Playing cards rarely form a card house
without your help card houses, once built,
usually fall apart.
So Whats This Got to do with Life?
Metabolism.involves E. transfers
Biological Reactions follow this format:
Reactants --> Products
A
Energy transfers go along with this

1. Reactants --> Products + Energy
2. Energy + Reactants --> Products
Energy from Food
Some living things

can convert sun E.
to food E.
Food E. transfers
from Plant to Deer
to Coyote
Each E. transfer
step loses ~90% to
heat (random
molecular motion).
How to measure the Energy in a

molecule?
Energy in a molecule (G) equals the energy in the

chemical bonds (H) minus the energy lost as heat
(S)
G= H - S
Also...The heat factor increases with Temp (T)
G = H ST
In Chemical Reactions, usually its the Change in E.
between Reactants and Products that matters
G = H - TS
Energy + Reactants --> Products
If products contain MORE energy than

reactants
Energy input is required for reaction
Reactions will NOT occur spontaneously
Termed Endergonic reactions
G value is positive
G = H - TS
Reactants --> Products + E
Products contain LESS energy than

reactants, excess E. is released
Energy is released to do work
Reactions will occur spontaneously
Termed Exergonic reactions
G value is negative
G = H - TS
Activation Energy
If so many reactions are exergonic

and release energy spontaneously,
why havent they already all
occurred?
They all require a bit of E. input
This is the Activation Energy
A kid on the slide needs a slight
push
Catalysts and Enzymes
The role of a catalyst is to lower the

amount of E. to push a reaction
forward
Catalysts may be biological or chemical
Biological catalysts are termed
enzymes
Catalysts (and enzymes) thus lower the
Activation E.
How do cells use the energy of chemical

bonds for work in the cell?
By creating an energy-rich compound for use now or stored for later use
Chief energy currency of cells; powers many cell reactions
Plant photosynthesis results in this compound being produced
A nucleotide composed of sugar, adenine and 3 PO 4
Energi Bebas (G)
Petunjuk arah reaksi biokimia

Tolok ukur : Perubahan Energi Bebas
Gibbs (G)
Reaksi Biokimia lebih banyak
mengacu kepada reaksi bersih
ketimbang kesetimbangan
Reaksi bersih memiliki G < 0
Perubahan Energi dan Proses Biokimiawi
Untuk memahami tujuan akhir metabolisme

perlu ditelaah hubungan antara perubahan
energi dan reaksi
Contoh : Isomerisasi glucose-6-phosphate
Glu-6-P Fruc-6-P dengan Go = 2.0 kJ/mol
Enzim : Glucose-6-Phosphate isomerase
Pemecahan ikatan yang sudah ada,
dilanjutkan dengan pembentukan ikatan yang
baru.
Energi Bebas Gibbs sebagai tolok ukur
G H TS
H : Perubahan enthalpy, energi
elektrostatik; misal energi ikatan
S : perubahan entropi, ketidak
teraturan
T : Temperatur absolut (oK)
Visualisasi Spontanitas
Reaksi eksoterm
belum tentu spontan
Contoh : Reaksi
peledakan H2 dgn O2
Reaksi endoterm, bisa
saja spontan
Contoh : Pelarutan
NaCl
Kontribusi dari
perubahan entropi
G dan Arah Reaksi Spontan
Pada kondisi P dan T yang tetap
G < 0; reaksi spontan dari kiri ke

kanan
G = 0; tepat dalam keadaan
setimbang
G > 0; reaksi spontan dari kanan ke
kiri, ditulis dalam arah kebalikannya
Ingat kembali Hukum Hess
Kelangsungan hidup butuh

kelangsungan reaksi kimia
Organisme yang mencapai

keadaan setimbang, mati
Reaksi setimbang, keluar
dari keadaan hanya dengan
perubahan eksternal
Bahan pangan,
menyediakan substrat untuk
reaksi yang menghasilkan
G bersih negatif
Ketergantungan G terhadap
konsentrasi
C
o'
G G
D
RT ln
A B
G : Perubahan energi bebas aktual pada kondisi reaksi,

termasuk konsentrasi
Go : Perubahan energi bebas standard, semua reaktan dan
produk berkonsentrasi 1 mol/l
Go : Perubahan energi bebas standard untuk Reaksi Biokimia.
Semua 1 mol/lt kecuali [H+] = [OH-] = 10-7, sehingga pH = 7
R : 8,314 J K-1mol-1 (konstanta gas)
T : 298oK (basis pengukuran Go'
[A],[B][C],[D] : konsentrasi aktual reaktan, produk
Cara Penyelesaian
Contoh Perhitungan
Glu-6-P Fruc-6-P Go = 2.0 kJ/mol

[Glu-6P] = 1,4 mM; [Fruc-6P] = 0,5 mM
3
(8,314)(298) 0,5x10
G 2,0
ln
3
1000
1,4 x10
G 2,0 (2,478)(1,030)
G 2,0 2,55 0,55kJ / mol
Jika [Glu-6-P] = 1,4 mM, berapa

[Fruc-6-P] maksimum agar reaksi
tetap berlangsung
Hitung [Fruc-6-P] agar G = 0
8,314 298
0 2,0
ln
1000
x
3
1,4 x10
x
2,0 2,478 ln
3
1,4 x10
2,0
3
ln x ln 1,4 x10
2,478
ln x 6,57 0,807 7,377
x 0,63x10 M 0,63mM
Jika [Fruc-6-P] = 0,5 mM,

berapa [Glu-6-P] minimum
agar reaksi tetap berlangsung
Hitung [Glu-6-P] agar G = 0
8,314 298 (0,5x10

0 2,0
ln
1000
x
3
0,5x10
2,0 2,478 ln
x
2,0
3
ln 0,5x10 ln x
2,478
ln x 7,60 0,807 6,79
x 1,12 x10 M 1,12mM
Hubungan Go dengan Keq
Berlaku pada saat sistem ekuilibrium
G 0
C D
dan K eq
A B
maka,
0 G RT ln K eq
0'
G RT ln K eq
o'
Hubungan Go dengan Keq
Contoh Soal
Hitunglah Keq untuk isomerasi Glu-6P dengan Go = 2,0 kJ/mol
G RT ln K eq
o'
(8,314)(298)
2,0
ln K eq
1000
2,0
ln K eq
0,807
2,478
K eq 0,45
Go diturunkan dari Keq
Citrate Isocitrate
G RT ln K eq
Keq = 0,075
o'
o'
8,314 298
ln 0,075
1000
o'
G 2,478 2,59
G 6,4kJ / mol
o'
Go dari Gof
G G
o'
o'
produk G f pereaksi
o'
Contoh : Hitunglah Go
Fumarate + H2O Malate
Gof (kJ/mol) Fumarate : -604,2
Gof (kJ/mol) H2O : -237,2
Gof (kJ/mol) Malate : -845,1
G dari G
o
G 845,1 604,2 237,2

o'
G 845,1 841,4
o'
G 3,7 kJ / mol
o'
Ilustrasi : Energetika reaksi Biokimia

Go berkisar antara - 60 hingga 30 kJ/mol
ATP + H2O ADP + HPO42Go = -30,3 kJ/mol
Berapa G hidrolisis ATP pada kondisi seluler ?
8,314 298 1,0x10 3 1,0x10 4

G 30,3
ln
1,0x10
G 30,3 [(2,478) x ln 1,0 x10 ]
3
1000
G 30,3 22,8 53,1 kJ/mol
G relativ besar; untuk apa ?
Pembentukan ikatan langsung oleh

DNA dan RNA polymerase
Konstraksi Otot - kerja mekanis
Transport aktif; memindahkan bahan
dari konsentrasi rendah ke
konsentrasi tinggi
Coupled reaction
Transport aktif melintasi membran
Pergerakan ion
melintasi membran
ATP dihidrolisis oleh
enzim ion-pumping
ATPase
Energi yang
dibebaskan digunakan
untuk memindahkan
K+ ke dalam, ditukar
dengan Na+
Mengapa ATP kaya energi ?
ATP : adenosine
triphosphate
Adenosine = adenin +
ribosa
Ikatan kaya energi
antara phosphate ke 1
dengan ke 2 dan antara
phosphate ke 2 dengan
ke 3
Berdasarkan jumlah
phosphate; ADP, AMP
Coupled Reaction
Reaksi A menjadi B
memiliki G yang positif
Tidak akan terjadi spontan
Dihubungan dengan reaksi
hidrolisis ATP yang G nya
sangat negatif
Reaksi bisa berlangsung
Tabel Go proses hidrolisis

Reaktan
Produk
PEP + H2O
Pyruvate + Pi
1,3 BPG + H2O 3PG + Pi
ATP + H2O
ADP + Pi
G-6-P + H2O
Glukosa + Pi
5-AMP + H2O Adenosine + Pi
Ikatan ester
Ikatan glycoside
Go
- 61,9 kJ/mol
- 54,5 kJ/mol
- 30,3 kJ/mol
- 13,8 kJ/mol
- 9,6 kJ/mol
- 19 kJ/mol
- 16 kJ/mol
Tabel Go proses hidrolisis

Reaktan
Produk
PEP + H2O
Pyruvate + Pi
1,3 BPG + H2O 3PG + Pi
ATP + H2O
ADP + Pi
G-6-P + H2O
Glukosa + Pi
5-AMP + H2O Adenosine + Pi
Ikatan ester
Ikatan glycoside
Go
- 61,9 kJ/mol
- 54,5 kJ/mol
- 30,3 kJ/mol
- 13,8 kJ/mol
- 9,6 kJ/mol
- 19 kJ/mol
- 16 kJ/mol
Contoh Perhitungan
Phosphorilasi Glukosa menjadi Glukosa-6Phosphate

Enzim : phosphotransferase atau kinase
Mentransfer satu Phosphate dari ATP ke
glukosa
ATP + glukosa Glukosa-6-P + ADP
G dihitung dengan menggunakan data dari
Tabel sesuai hukum Hess
Penggunaan Tabel
ATP H 2 O ADP Pi
G 30,3 kJ / mol
o'
Glu Pi Glu 6 P H 2 O G o' 13,9 kJ/mol

ATP Glu Glu - 6 - P H 2 O G -16,4 kJ/mol
o'
Senyawa yang di bawah ATP memindahkan

Phosphate dari ATP ke akseptornya.
Senyawa yang di atas ATP, berperan dalam
pembentukan ATP dari P dan ADP.
Bagaimana kaitannya dengan Metabolisme ?
Resume
Molekul Kompleks :
Protein, Polisakarida,
DNA, RNA, Fats
Molekul sederhana :
bahan pembangunnya
Making ATP :
pembentukan ATP dari
ADP dan P
Konsumsi ATP :
pemutusan salah satu
ikatan yang kaya
energi
Jalur Katabolik dan Anabolik
Sebagian besar
energi ikatan kimia
yang tersimpan
dalam bahan pangan
terbebas sebagai
panas.
Bahan pangan yang

dikatabolisme lebih
besar dari yang
dianabolisme.
Redoks; Mengapa harus dipahami ?
Proses katabolik melibatkan berbagai

tahap oksidasi
Proses biokimia melibatkan energi
yang banyak, strategi untuk
menangkap energi secara efisien
harus ada.
Kebanyakan proses oksidasi-reduksi
terkait dengan produksi ATP
Electron Energies
In Oxidation/Reduction
reactions e- are passed
from one atom to
another
Oxidized atom gives eto reduced atom
Reduced form now has
more energy than
oxidized one
The amount of E
passed on by edepends on how far it
was from the nucleus
Beberapa Terminologi
Oksidase : enzim yang mengkatalisis

oksidasi langsung oleh O2.
Dehidrogenasi : oksidasi dengan

menghilangkan 2 atom H dari substrat.
Butuh penerima hidrogen, yang bisa
didaur ulang melalui phosphorilasi
oksidatif.
Nicotinamide Adenine Dinucleotide, NAD+
Koenzim, banyak berperan

sebagai akseptor hidrogen
dalam oksidasi
Didaur ulang di sel yang
sama; tidak terkonsumsi
Struktur : Nicotinamide,
Adenine, Phosphate,
Ribose
Terlibat dalam redoks,
hanya nicotinamide
Reaksi NAD+ NADH
NAD+ menerima 2
atom H atom, d.h.i.
2 H+ and 2 elektron
dari substrat yang
mengalami oksidasi.
2 elektron dan satu
H+ membentuk
NADH, satu proton
dibebaskan
Beberapa Reaksi yang terangkai

dengan NAD+
NADH didaur ulang menjadi NAD+ melalui fosforilasi oksidatif,

energi yang tertangkap untuk sintesis 2.5 ATP/NADH.
Nicotinamide Adenine Dinucleotide

Phosphate, NADP+
Sama dengan NAD+, tetapi dengan

tambahan gugus fosfat di 2'-O dari
adenosin.
Tidak ada perbedaan reaktifitas kimiawi
komponen nicotinamide.
Tambahan fosfat sebagai penanda untuk
dikenali oleh enzim
NADPH reducing agent untuk anabolik,
tidak didaur ulang lewat fosforilasi oksidatif
Flavin Adenine Dinucleotide, FAD
Koenzim kedua
Tetap terikat dengan
enzim, daur ulang
internal; gugus
prosthetic enzim
Struktur : flavin ring,
ribitol pengganti ribose,
2 gugus fosfat,
adenosin.
Jika satu fosfat flavin
mononucleotide, FMN.
Reaksi FAD FADH2
FAD menerima 2 atom H (2 H+ dan 2 elektron) yang diikatkan

ke atom N
FADH2 didaur ulang menjadi FAD melalui fosforilasi oksidativ,
energi yang tertangkap digunakan untuk sintesis 1.5
ATP/FADH2.
FAD memindahkan atom H dari C

yang jenuh
Salah satu reaksi dalam siklus TCA

Mengapa bukan NAD+ ?
Alasan energetika
Energetika reaksi Redoks
Tolok ukur : Potensial Reduksi Standar (Eo)

Eo : potensial reduksi standar pada pH = 0
Eo : potensial reduksi standar untuk reaksi
biokimia, pada pH = 7
Dibuat Tabel setengah reaksi, yang harus
dikombinasikan dengan reaksi lain, karena
elektron bebas tidak bisa exist di dalam
larutan.
Tabel Potensial Reduksi Standar

Reaktan
Asetat + 2H+ + 2eNAD+ + 2H+ + 2ePiruvat + 2H+ + 2eFumarat + 2H+ + 2eFAD + 2H+ + 2e O2 + 2H+ + 2e-
Produk
Acetaldehid + H2O
NADH + H+
Laktat
Suksinat
FADH2
H2O
Eo (v)
- 0,57
- 0,321
- 0,185
+ 0,031
+ 0,10
+ 0,815
Contoh Reaksi Kombinasi
NAD 2H 2e NADH H
Laktat
NAD Laktat
Piruvat 2H 2e
NADH H Piruvat
Enzim yang berperan : lactate

dehydrogenase
Energetika reaksi kombinasi

NAD 2H 2e NADH H
E o' 0,321
Laktat
Piruvat 2H 2e
E o' 0,185
NAD Laktat
NADH H Piruvat
E o' 0,136
Gunakan Tabel Potensial Reduksi Standar

Tanda berbalik, jika reaksi berubah arah
Potensial dan Energi Bebas
G n F E
o'
o'
G n F E
n : jumlah elektron yang terlibat

F : konstanta Faraday; 96 485 Coulomb/mol
Perhatikan : coulomb x volts = joules
Contoh : Lactate dehydrogenase
G nFE
o'
o'
G 2 96485 coulomb/mol 0,136 v

o'
G 26244 Joules/mol
o'
Sangat positif; Reaksi yang terjadi

adalah dalam arah kebalikannya
Persamaan Nernst
Hubungan potensial standar dan aktual

berdasarkan konsentrasi reaktan dan produk.
Untuk E, atau
Contoh Soal : Lactate dehydrogenase
Kondisi :
[NADH] / [NAD+] = 0.0020,

[lactate] = 2.0 mM
[pyruvate] = 0.020 mM
Bagaimana pengaruhnya terhadap E dan E
Pendekatan 1 : Hitung E dari masing-masing

setengah reaksi
Pendekatan 2 : Hitung E dari reaksi kombinasi
Pendekatan I : E setengah reaksi

reduksi
NAD Laktat NADH H Piruvat

E E acceptor E donor
E 0,241 0,244 0,003 v
Pendekatan 2 : E reaksi kombinasi
8,314 298
E 0,136
2 96485
0,00002
ln 0,002
0,002
E 0,136 0,01264 10,82

E 0,003 volts
Resume
Oxidation-reduction reactions often release significant

quantities of energy in biochemical processes. Many
reactions are catalysed by enzymes called
dehydrogenases, and these require hydrogen acceptors
such and NAD+ or FAD.
Reoxidation of the resulting NADH or FADH2 can be linked
to ATP synthesis.
Energetics of oxidation-reduction reactions are
determined through standard reduction potentials and the
Nernst equation.

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Termodinamika Reaksi

Termodinamika Reaksi Biokimia; ITP 240

Termodinamika Reaksi Biokimia; ITP 240

Tetapan yang sering dipakai

Termodinamika Reaksi Biokimia; ITP 240

Energy & Metabolism

All living things require energy

Termodinamika Reaksi Biokimia; ITP 240

Energi Potensial dan Kinetik

Bentuk : Mechanical, Sound, Electricity, Light,

Termodinamika Reaksi Biokimia; ITP 240

Useful way to study energy because all

Termodinamika Reaksi Biokimia; ITP 240

Ultimately, all E. for life on

Termodinamika Reaksi Biokimia; ITP 240

Energy from Chemical Bonds

Chemicals may be considered from a potential

Termodinamika Reaksi Biokimia; ITP 240

Example of the Energy in Covalent Bonds

Termodinamika Reaksi Biokimia; ITP 240

Energy Loss in each Energy Transfer

Termodinamika Reaksi Biokimia; ITP 240

The Laws of Thermodynamics

The First Law is also stated as energy is conserved.

Termodinamika Reaksi Biokimia; ITP 240

How do we know this?

Termodinamika Reaksi Biokimia; ITP 240

The First Law of Thermodynamics

The first law is very simple: You can't create or

Termodinamika Reaksi Biokimia; ITP 240

The Second Law

Energy spontaneously tends to flow only from

Termodinamika Reaksi Biokimia; ITP 240

The Second Law

Energy is constantly being converted

Termodinamika Reaksi Biokimia; ITP 240

Termodinamika Reaksi Biokimia; ITP 240

So Whats This Got to do with Life?

Energy transfers go along with this

Termodinamika Reaksi Biokimia; ITP 240

Energy from Food

Some living things

Termodinamika Reaksi Biokimia; ITP 240

How to measure the Energy in a

Energy in a molecule (G) equals the energy in the

Termodinamika Reaksi Biokimia; ITP 240

Energy + Reactants --> Products

If products contain MORE energy than

Termodinamika Reaksi Biokimia; ITP 240

Reactants --> Products + E

Products contain LESS energy than

Termodinamika Reaksi Biokimia; ITP 240

If so many reactions are exergonic

Termodinamika Reaksi Biokimia; ITP 240

Catalysts and Enzymes

The role of a catalyst is to lower the

Termodinamika Reaksi Biokimia; ITP 240

How do cells use the energy of chemical