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What does using operator keyword with object mean?

#include

class Account{
public:
explicit Account(double b): balance(b){}
Account& operator += (double b){
balance += b;
return * this;
}
friend Account& operator += (Account& a, Account& b);
friend std::ostream& operator << (std::ostream& os, const Account& a);
private:
double balance;
};

Account& operator += (Account& a, Account& b){
a.balance += b.balance;
return a;
}

std::ostream& operator << (std::ostream& os, const Account& a){
os << a.balance;
return os;
}

int main(){
std::cout << std::endl;
Account acc1(100.0);
Account acc2(100.0);
Account acc3(100.0);
acc1 += 50.0;
acc1 += acc1;
acc2 += 50.0;
acc2 += acc2;
acc3.operator += (50.0);
//acc3.operator += (acc3); ERROR
std::cout << "acc1: " << acc1 << std::endl;
std::cout << "acc2: " << acc2 << std::endl;
std::cout << std::endl;
}

acc3.operator += (50.0);
//acc3.operator += (acc3); ERROR
In the above code, what does using .operator with a object mean. and why second line shows an error?